EP1776391A1 - Copolymeres, leur preparation et leur utilisation - Google Patents

Copolymeres, leur preparation et leur utilisation

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Publication number
EP1776391A1
EP1776391A1 EP05778453A EP05778453A EP1776391A1 EP 1776391 A1 EP1776391 A1 EP 1776391A1 EP 05778453 A EP05778453 A EP 05778453A EP 05778453 A EP05778453 A EP 05778453A EP 1776391 A1 EP1776391 A1 EP 1776391A1
Authority
EP
European Patent Office
Prior art keywords
weight
ethylenically unsaturated
carboxylic acid
unsaturated carboxylic
comonomers
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Withdrawn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
EP05778453A
Other languages
German (de)
English (en)
Inventor
Gerhard Wolf
Matthias KLÜGLEIN
Stephan Hüffer
Susanne Petrovic
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 EP1776391A1 publication Critical patent/EP1776391A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
    • 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
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/02—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of acids, salts or anhydrides
    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/4935—Impregnated naturally solid product [e.g., leather, stone, etc.]

Definitions

  • Copolymers their preparation and use
  • the present invention relates to copolymers prepared by copolymerization in at least two stages, characterized in that in one step
  • (B) is reacted with a further comonomer or a further mixture of comonomers comprising (b1) 0 to 30% by weight of at least one ethylenically unsaturated carboxylic acid,
  • the present invention relates to a process for the preparation of copolymers according to the invention and to uses of the copolymers according to the invention.
  • EP 0 418 661 describes the use of copolymers containing 50 to 90% by weight of C 8 -C 40 -alkyl (meth) acrylates and / or vinyl esters of C 8 -C 40 -carboxylic acids and
  • copolymers described are suitable in at least partially neutralized form in aqueous solution or aqueous dispersion for the hydrophobization of leather.
  • the resulting leathers are unsatisfactory in terms of their grain firmness.
  • WO 95/20056 describes aqueous polymer dispersions in which the polymer is in each case composed of 50 to 90% by weight of alkyl acrylate and 10 to 50% by weight.
  • (Meth) acrylic acid is obtained, and its use for fats and filling of leather countries described.
  • the polymer dispersions prepared according to WO 95/20056 also show defects in the grain-tightness of the leather.
  • the ability to combine with other products used in tanning or retanning is limited and can lead to negative results in terms of softness, fullness, coloration and, in particular, grain firmness.
  • the object was to provide leather treatment compositions which provide improved leather in terms of softness, fullness, dyeability and grain firmness and which can be used well in combination with leather treatment agents known from the prior art. It was a further object to provide a process for the production of leather treatment agents. A further object was to provide uses for treated leathers.
  • copolymers defined above were found.
  • the copolymers according to the invention are prepared by copolymerization in at least two stages, ie by a multistage process, for example a two-stage process or a three-stage process or a four-stage process.
  • Copolymers of the invention are obtained by reacting in one stage
  • (B) with a further comonomer or another mixture of Comonome ⁇ reindeers comprising (b1) 0 to 30 wt .-%, preferably up to 20 wt .-% of at least one ethylenically unsaturated carboxylic acid, (b2) 70 to 100 wt. -%, preferably 80 to 100 wt .-% of at least one
  • R 1 is selected from hydrogen
  • R 2 selected from
  • C 1 -C 0 -alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec- Pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-Hexyi, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, be ⁇ particularly preferably d -CrAlkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl,
  • R 2 is hydrogen and R 1 is hydrogen or methyl.
  • ethylenically unsaturated carboxylic acid (a1) as acrylic acid, methacrylic acid or mixtures of acrylic acid and methacrylic acid.
  • R 3 is selected from C 1 -C 22 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec.
  • -Pentyl neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, n-eicosyl, more preferably n-butyl and 2-ethylhexyl.
  • R 4 is selected from hydrogen
  • C t -C -alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl , neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl; particularly preferably C 1 -C 4 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl,
  • R 5 is hydrogen and R 4 is hydrogen or methyl.
  • R 5 is hydrogen and R 4 is hydrogen or methyl and R 3 is selected from methyl, ethyl, n-butyl and 2-ethylhexyl.
  • Suitable further ethylenically unsaturated compound (a3) are, for example:
  • Vinyl esters of formic acid or of C 1 -C 6 -alkylcarboxylic acids in particular vinyl acetate,
  • the formed (co) polymer can be isolated and purified. It is also possible to mechanically work the formed (co) polymer, for example to comminute it.
  • the Aufreini ⁇ conditions of the formed (co) polymer dispensed with and sets it in a further stage with
  • (b2) 70 to 100 wt .-%, preferably 80 to 100 wt .-% at least. a C 1 -C 22 -alkyl ester of at least one ethylenically unsaturated carboxylic acid, (b3) 0 to 10% by weight, preferably 0.5 to 5% by weight of at least one further ethylenically unsaturated compound,
  • Ethylenically unsaturated carboxylic acid (b1) are preferably selected from those of the general formula I.
  • ethylenically unsaturated carboxylic acid (a1) and ethylenically unsaturated carboxylic acid (b1) are the same or different.
  • methacrylic acid as ethylenically unsaturated carboxylic acid (a1)
  • acrylic acid as ethylenically unsaturated carboxylic acid (b1).
  • ethylenically unsaturated carboxylic acid (a1) and ethylenically unsaturated carboxylic acid (b1) are each the same and selected from (meth) acrylic acid.
  • C 1 -C 22 -alkyl esters of ethylenically unsaturated carboxylic acid (b2) are preferably selected from those of the general formula II. It is possible that C 1 -C 22 -alkyl esters of ethylenically unsaturated carboxylic acid (a2) and C 1 -C 22 -alkyl esters of ethylenically unsaturated Carboxylic acid (b2) are the same or different. Thus, for example, C r C 22 alkyl esters of ethylenically unsaturated carboxylic acid (a2) (meth) acrylate and choose as CrC 22 -A!
  • Alkyl ester of ethylenically unsaturated carboxylic acid (b2) (meth) acrylic acid 2-ethylhexylester or (meth ) n-butyl acrylate. It is also possible to use (meth) acrylic acid 2-ethylhexyl ester or (meth) acrylic acid as the C 1 -C 22 -alkyl ester of ethylenically unsaturated carboxylic acid (a2). acid-n-butyl ester and as C r C 22 alkyl esters of ethylenically unsaturated carboxylic acid (b2) methyl (meth) acrylate.
  • Ci-C 22 alkyl esters of ethylenically unsaturated carboxylic acid (a2) and C r C 22 alkyl esters of ethylenically ungesreli ⁇ -saturated carboxylic acid (b2) each identical and selected for example from (meth) methyl acrylate, (Meth) acrylic acid 2-ethylhexyl ester and (meth) acrylic acid n-butyl ester.
  • step (B) mixtures of two or more different C 1 -C 22 alkyl esters of ethylenically unsaturated carboxylic acid (b2) may be used, for example a mixture of 50% by weight of ethyl acrylate and 50% by weight of n-butyl acrylate.
  • Suitable further ethylenically unsaturated compound (b3) are, for example:
  • Vinyl esters of formic acid or of C 1 -C 6 -alkylcarboxylic acids in particular vinyl acetate,
  • C-C double bond preferably vinylsulfonic acid or 2-acrylamido-2-methylpropanesulfonic acid
  • C 1 -C 22 -alkyl esters of ethylenically unsaturated carboxylic acid (d) are preferably selected from those of the general formula II. It is possible for C 1 -C 22 -alkyl esters of ethylenically unsaturated carboxylic acid (d) and C 1 -C 22 -alkyl esters of ethylenically unsaturated carboxylic acid (a2) or (b2) are identical or different.
  • C 1 -C 4 -alkyl esters of ethylenically unsaturated carboxylic acid (d) (meth) acrylate and, as C 1 -C 4 -alkyl esters of ethylenically unsaturated carboxylic acid (a2) or (b2), (meth) acrylic acid 2-ethylhexyl ester or (meth) acrylic acid n-butyl.
  • -C 22 alkyl esters of ethylenically unsaturated carboxylic acid (d), and -C 22 alkyl esters of ethylenically ungesreli ⁇ -saturated carboxylic acid (a2) and (b2) each identical and selected for example from (meth) methyl acrylate, (Meth) acrylic acid 2-ethylhexyl ester and (meth) acrylic acid n-butyl ester.
  • the mass of monomer or comonomers from stage (A) to the mass of monomer or comonomers from stage (B) behaves as 1 to 100 to 1 to 1, preferably 1 to 20 to 1 to 2.
  • the masses of the sum of monomers or comonomers of (A) and (B) can behave to the mass of (C) as 50 to 1 to 1 to 1, preferably 20 to 1 to 2 to 1.
  • the difference of the glass transition temperatures T 9 of polymer or random copolymer from stage (A) and polymer or random copolymer from stage (B) is at least 80 ° C., preferably at least 100 ° C.
  • the glass transition temperatures T 9 are calculated according to the Fox equation or determined by DSC (Differential Thermal Analysis, Differential Scanning Calorimetry) in accordance with DIN 53765, for example.
  • Polymer or random copolymer from stage (A) is understood to mean polymer which can be isolated after carrying out stage (A).
  • Polymer or random copolymer from stage (B) are understood to mean those polymers or copolymers which are obtained by polymerization or copolymerization of the (co) monomers (b2), optionally (b1) and, if appropriate, (b3) in the absence of polymer Stage (A) are available.
  • polymer from step (A) has a molecular weight M w in the range from 30,000 g / mol to 750,000 g / mol, preferably in the range from 50,000 g / mol to 550,000 g / mol.
  • polymer or random copolymer from step (B) has a molecular weight M w in the range from 1000 g / mol to 200,000 g / mol, preferably in the range from 2000 g / mol to 100,000 g / mol.
  • the polydispersity MjM n copolymers of the invention may be in the range of 1, 1 and 40, preferably from 2 to 20
  • Another object of the present invention is a process for the preparation of novel copolymers according to the invention also mentioned below manufacturing method.
  • Another object of the present invention is a process for the preparation of copolymers, characterized in that in one step
  • (Co) polymer from stage (A) can be prepared by any methods known per se from polymer chemistry, for example by solution polymerization, precipitation polymerization, bulk polymerization, suspension polymerization and, in particular, emulsion polymerization.
  • (co) polymer is prepared from step (A) using at least one initiator.
  • At least one initiator may be a peroxide.
  • suitable peroxides are alkali metal peroxodisulfates, e.g. Sodium peroxodisulfate, ammonium peroxodisulfate, hydrogen peroxide, organic peroxides such as diacetyl peroxide, di-tert-butyl peroxide, diamyl peroxide, dioctanoyl peroxide, didecanoyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, bis (o-toloyl) peroxide, succinyl peroxide, tert-butyl peracetate, tert.
  • alkali metal peroxodisulfates e.g. Sodium peroxodisulfate, ammonium peroxodisulfate, hydrogen peroxide
  • azo compounds such as azobisisobutyronitrile, azobis (2-amidopropane) dihydrochloride and 2,2'-azobis (2-methylbutyronitrile).
  • Redox initiators are also suitable, for example from peroxides and oxidizable sulfur compound.
  • peroxides and oxidizable sulfur compound Very particular preference is given to systems composed of acetone bisulfite and organic peroxide such as tert-C 4 H 9 -OOH, Na 2 S 2 O 5 (sodium disulfate) and organic peroxide such as tert-C 4 H 9 -OOH or combinations of alkali metal salts of HO-CH 2 SO 2 H and organic peroxide such as tert-C 4 H 9 -OOH.
  • systems such as ascorbic acid / H 2 O 2 are particularly preferred.
  • initiator is used in amounts of from 0.1 to 20% by weight, preferably from 0.2 to 15% by weight, calculated on the mass of all comonomers.
  • temperatures in the range from 20 to 100 ° C., preferably from 50 to 90 ° C. can be selected as the (co) polymerization temperature.
  • the selected temperature is dependent on the decay characteristic of the initiator used.
  • the pressure conditions are generally not critical, suitable, for example, pressures in the range of atmospheric pressure to 10 bar.
  • At least one emulsifier which may be anionic, cationic or nonionic.
  • Suitable nonionic emulsifiers are ethoxylated mono-, di- and tri-alkylphenols (degree of ethoxylation: 3 to 50, alkyl radical: C 4 -C 2) and also ethoxylated fatty alcohols (degree of ethoxylation: 3 to 80; alkyl radical: C 8 to C 3 S) - Examples are the Lutensol ® brands from BASF Aktiengesellschaft and the Triton ® grades from Union Carbide.
  • Suitable anionic emulsifiers are, for example, alkali metal and ammonium salts of alkyl sulfates (alkyl radical: C 8 to C 12 ), of sulfuric monoesters of ethoxylated alkanols (degree of ethoxylation: 4 to 30, alkyl radical: C 12 -C 18 ) of ethoxylated alkylphenols (degree of ethoxylation: 3 to 50, alkyl radical : C 4 -C 12 ), of alkylsulfonic acids (alkyl radical: C 12 -C 18 ), of alkylarylsulfonic acids (alkyl radical: C 9 -C 18 ), of sulfosuccinates such as, for example, monobasic acid mono- and diesters, and of carboxylates, for example N-oleylsarcosine ,
  • Suitable cationic emulsifiers are generally C 6 -C 18 -alkyl-, aralkyl- or heterocyclic radical-containing primary, secondary, tertiary or quaternary ammonium salts, alkanolammonium salts, pyridinium salts, imidazolinium salts, oxazolinium salts, morpholinium salts, thiazolinium salts and salts of amine oxides, quinolinium salts , Isoquinolinium salts, tropylium salts, sulfonium salts and phosphonium salts.
  • Examples include dodecylammonium acetate or the corresponding hydrochloride, the chlorides or acetates of the various 2- ( ⁇ /, ⁇ /, / V-trimethylammonium) ethylparaffinklar, ⁇ / -Cetylpyridiniumchlorid, / V-Laurylpyri- diniumsulfat and ⁇ / - Cetyl- ⁇ /, ⁇ /, / V-trimethylammonium bromide, ⁇ / -dodecyl- ⁇ /, ⁇ /, ⁇ / -trimethylammonium bromide, ⁇ /, ⁇ / -distearyl- ⁇ /, ⁇ / -dimethylammonium chloride and the gemini Surfactant ⁇ /, / V- (lauryldimethyl) ethylenediamine dibromide. Numerous other examples can be found in H. Stumblee, Ten,
  • the amount of emulsifier is chosen such that the mass ratio between monomer or comonomer on the one hand and emulsifier on the other hand is greater than 1, preferably greater than 10 and particularly preferably greater than 20.
  • the reaction is preferably carried out in the absence of oxygen, for example in a nitrogen or argon atmosphere, preferably in a nitrogen stream.
  • regulators for the preparation of (co) polymer in stage (A) for example C 1 to C 4 aldehydes, formic acid and compounds containing organic SH groups, such as 2-mercaptoethanol, 2-mercaptopropanol, mercaptoacetic acid, tert Butyl mercaptan, n-dodecylmercaptan.
  • Polymerization regulators are generally used in amounts of from 0.1 to 10% by weight, based on the total weight of the (co) monomers used. Preference is given to working without the use of controllers.
  • the duration of the (co) polymerization in step (A) is generally from 30 minutes to 10 hours, preferably from 1 to 5 hours, more preferably from 3 to 5 hours.
  • step (A) After addition of (a1), if appropriate (a2) and optionally (a3), it is possible to react further until (a1), optionally (a2) and optionally (a3) have been copolymerized completely or at least to a total of at least 50% by weight ie until completion of the copolymerization in step (A). However, it is also possible to proceed immediately after the addition of monomer or comonomers from stage (A) and starting (co) polymerization with stage (B).
  • step (B) Upon completion of the (co) polymerization, step (B) can be immediately followed. After completion of the (co) polymerization, it is possible first to isolate and, if necessary, to purify the (co) polymer produced and then to add step (B). It is also possible to partially or quantitatively neutralize the carboxyl groups of (co) polymer prepared according to step (A) by addition of, for example, a basic alkali metal compound or at least one amine.
  • step (B) the (co) polymer obtained and optionally isolated and / or purified and / or partially or completely neutralized after step (A) is reacted with a further monomer or a further mixture of comonomers.
  • a further mixture of comonomers is also referred to below if in step (A) only one ethylenically unsaturated carboxylic acid (a1) has been polymerized.
  • a further monomer or a further mixture of comonomers is also used if the same comonomers are used in stages (A) and (B), but in different proportions.
  • the reaction in step (B) is preferably carried out as a free-radical (co) polymerization, for example in the form of a bulk or solution polymerization and particularly preferably in the form of an emulsion polymerization. It is very particularly preferred to do without the isolation of (co) polymer from stage (A) and to continue working in the same dispersion or solution or emulsion.
  • Emulsifiers may be the same or different from the emulsifier or emulsifiers of step (A) or may.
  • step (B) it is possible to add one or more regulators before, after and / or during the addition of (b2), optionally (b1) and optionally (b3), the regulator (s) being identical or different from the regulator (s) of step (A ) can or can be.
  • the regulator (s) being identical or different from the regulator (s) of step (A ) can or can be.
  • temperatures in the range from 20 to 100 ° C., preferably from 50 to 90 ° C. can be selected as the (co) polymerization temperature in step (B).
  • the selected temperature depends on the decay characteristic of the initiator used.
  • step (B) The pressure conditions in step (B) are generally not critical, for example pressures in the range from atmospheric pressure to 10 bar are suitable.
  • the duration of the (co) polymerization in stage (B) is generally from 30 minutes to 10 hours, preferably from 1 to 8 hours, more preferably from 90 minutes to 6 hours.
  • step (C) After step (B), after completion of step (B) it is possible first to isolate and purify a copolymer of the invention and then to carry out step (C) by reaction with (d). However, in another variant, it is possible to continue working without isolation of copolymer of the invention and to carry out stage (C) by reacting with (d).
  • emulsifier (s) may be identical or different from the emulsifier or emulsifiers from stage (A) or (B) or can.
  • regulator (s) may be the same as or different from the regulator (s) of stage (A) and (B), respectively can.
  • step (C) can be, for example, Temperatu ⁇ ren is in the range of 20 to 100 0 C, preferably 50 to select 90 0 C.
  • the selected temperature is dependent on the decay characteristic of the initiator used.
  • step (C) The pressure conditions in step (C) are generally not critical, for example, pressures in the range of atmospheric pressure to 10 bar are suitable.
  • the duration of the (co) polymerization in step (C) is generally from 30 minutes to 10 hours, preferably from 1 to 5 hours.
  • step (B) it is possible for the polymer or copolymer from step (B) to be grafted onto the polymer or copolymer from stage (A). It is also possible for the polymer or copolymer from stage (B) to encase or physically penetrate the polymer (s) or the copolymer (s) from step (A), but that no covalent linkage takes place.
  • step (B) If the addition of monomer or comonomer from step (B) has begun before monomer or comonomers from step (A) have completely reacted, a mixture of copolymers having a different comonomer incorporation ratio is obtained.
  • the mixture obtainable in this way can then contain, for example, copolymers which are composed of comonomers of stage (A), which are composed of copolymers of stages (A) and (B) and which are composed of comonomers of stage (B).
  • copolymer according to the invention has been carried out as a solution polymerization, it is possible to isolate copolymer according to the invention by evaporation of the solvent, for example.
  • the inventive production of copolymer according to the invention has been carried out as an emulsion polymerization, it is obtained in the form of aqueous dispersions or emulsions, which are also the subject of the present invention, and from which it can be isolated, for example, by filtration or by evaporation of the water in which the evaporation can be carried out, for example, by spray drying in one or more spray towers.
  • aqueous dispersions or emulsions which are also the subject of the present invention, and from which it can be isolated, for example, by filtration or by evaporation of the water in which the evaporation can be carried out, for example, by spray drying in one or more spray towers.
  • a copolymer according to the invention is neutralized partially or completely, for example with a basic alkali metal compound or with amine.
  • basic alkali metal compounds are alkali metal hydroxide such as NaOH and KOH, alkali metal carbonate such as Na 2 CO 3 and K 2 CO 3 , alkali metal bicarbonate such as
  • Aqueous dispersions or emulsions according to the invention may have a solids content in the range from 1% by weight to 70% by weight, preferably from 20% by weight to 60% by weight.
  • Another object of the present invention is the use of inventive copolymers, for example in the form of aqueous dispersions of the invention, for the production of leather.
  • a further subject of the present invention is a process for the production of leather using copolymers according to the invention, for example in the form of aqueous dispersions according to the invention.
  • leather is animal skin tanned with the aid of chrome tanning agents (wet-blue) or semi-finished products.
  • leather is leather made of chromium-free tanned animal skin (wet-white) or semi-finished products.
  • Copolymers according to the invention for example in the form of dispersions according to the invention, can be used in tanning and preferably in retanning, in the following referred to as tanning process or inventive retanning process. It is possible to use dispersions according to the invention in a separate treatment step
  • the tanning process according to the invention is generally carried out by adding er ⁇ inventive dispersion or inventive copolymer in one portion or in several portions immediately before or during tanning.
  • the tanning process according to the invention is preferably carried out at a pH of from 2.5 to 8, preferably from 3 to 5.5.
  • the pH can be increased by adding blunting agents by about 0.3 to three units.
  • the tanning process according to the invention can be started at a pH in the range from 4 to 8, and copolymer according to the invention can be prepared by addition of an acidic component such as formic acid at a pH in the range from 3 to 5 , 5 fix.
  • the novel tanning process is generally carried out at temperatures of 10 to 45 ° C, preferably 0 to 30 C at 20th Has proven useful a duration of 10 minutes to 12 hours, preferably one to three hours.
  • the tanning process according to the invention can be carried out in any conventional tanning vessel, for example by walking in barrels or in rotated drums.
  • the dispersion or copolymer of the invention is used together with one or more conventional tanning agents, for example with chrome tanning agents, mineral tannins, preferably with syntans, polymer tanning agents or vegetable tanning agents, as described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, Volume A15, pages 259 to 282 and especially page 268 ff., 5th Edition, (1990), Verlag Chemie Weinheim.
  • one or more conventional tanning agents for example with chrome tanning agents, mineral tannins, preferably with syntans, polymer tanning agents or vegetable tanning agents, as described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, Volume A15, pages 259 to 282 and especially page 268 ff., 5th Edition, (1990), Verlag Chemie Weinheim.
  • the novel dispersion or copolymer according to the invention is used together with fatliquoring agents such as native triglycerides, white oil, paraffin, wax, silicone oil, and also emulsifiers.
  • fatliquoring agents such as native triglycerides, white oil, paraffin, wax, silicone oil, and also emulsifiers.
  • the process according to the invention for treating leather can preferably be carried out as a process for retanning leather using a dispersion according to the invention or copolymer of the invention.
  • the retanning process according to the invention is based on conventional, i. For example, with chrome tanning agents, mineral tannins based on Al, Ti, Zr, Fe and Si, preferably semi-finished products tanned with polymer tanning agents, aldehydes, vegetable tannins, syntans or resin tanning or semi-finished products according to the invention.
  • copolymer according to the invention is allowed to act on semi-finished products.
  • the retanning process according to the invention can be carried out under otherwise customary conditions. It is expedient to choose one or more, ie 2 to 6, single action steps and to rinse with water between the reaction steps.
  • the structure is Tempera ⁇ during the individual treatment respectively in the range of 5 to 60 0 C, Jack ⁇ Trains t 20 to 45 ° C. From 0.5 to 40% by weight, preferably from 2 to 20% by weight, of the dispersion or copolymer of the invention, based on the shaved weight, can be used in the retanning process according to the invention.
  • dispersion or copolymer according to the invention can be used in the tanning or retanning process according to the invention during the retanning, for example fatliquors, polymer tanning agents, acrylate- and / or methacrylate-based or silicone-based retanning agents based on Resin and Vegetabilgerbstoffen, fillers, leather dyes or emulsifiers or combinations of at least 2 of the aforementioned substances.
  • the treatment according to the invention leather is hydrophobicized or greased, that is, there is an improved fiber insulation. On the one hand, this improves the softness of the leather and, on the other hand, reduces the specific weight of the leather, resulting in advantages in terms of comfort when using leather produced according to the invention in furniture, car upholstery, clothing upper leather such as, for example, shoe upper leathers.
  • the inventive treatment of the leather on the basis of wet-white or on the basis of wet-blue produced leathers, further improves the fullness and the tangible properties of leather produced according to the invention.
  • grip includes a soft, not fat-heavy, velvety surface grip, which combined with an inner softness of the leather leads to an optimal overall impression of the leather.
  • the inventive treatment of the leather, the grain tightness According to the invention of leather produced is improved, that is a so-called undesirable to those skilled Doppelnosutmaschine the leather is avoided, the scars' is snug and does not tend to Splisstechnik.
  • Another aspect of the present invention is leather, for example leather based on wet-white or wet-blue and particularly preferably leather on the basis of wet-white, produced by the tanning process according to the invention or the retanning process according to the invention or by a combination of the novel process
  • the tanning process and the retanning process according to the invention are characterized by an overall advantageous quality, for example they have a particularly pleasant feel and are very soft and full.
  • the leathers according to the invention contain a copolymer described above which has penetrated particularly well into micro-regions of the elementary fibers.
  • Another aspect of the present invention is the use of leather according to the invention, for example leather of the invention based on wet-white or wet-blue, for the production of items of clothing such as, for example, shoes or furniture or car upholstery.
  • Another aspect of the present invention is a Process for the production of articles of clothing such as, for example, shoes, furniture or automotive parts such as car upholstery using leather according to the invention, for example leathers based on wet white or wet blue according to the invention.
  • garment items are, for example, jackets, trousers, belts or suspenders, and in particular shoes, in particular shoe soles, shoe upper leather, shoe lining material and shoe insole.
  • furniture is to be understood as meaning all such furniture which contains components of leather, for example as a seat or on armrests.
  • Examples include seating, such as armchairs, chairs, sofas.
  • Car parts are exemplified by car upholstery such as car seats and furthermore steering wheels and dashboards and door interior parts.
  • Another aspect of the present invention are garments comprising or made of leather according to the invention.
  • Another aspect of the present invention are furniture comprising or made of leathers according to the invention.
  • Another aspect of the present invention are car parts containing or manufactured from leathers according to the invention.
  • a further aspect of the present invention are formulations comprising at least one copolymer according to the invention and at least one hydrophobic or amphiphilic substance selected from oils, waxes and synthetic polymers.
  • a further aspect of the present invention are formulations containing at least one copolymer according to the invention, at least one hydrophobic or amphiphilic substance selected from oils, waxes and synthetic polymers, and at least one emulsifier.
  • At least one hydrophobic substance selected from oils and waxes, may be a carbon-based compound, for example natural or synthetic wax, virgin or synthetic oil or native or synthetic fat.
  • Examples of natural waxes include beeswax, cork wax, montan waxes or carna ⁇ bawachs.
  • Examples of synthetic waxes are polyethylene waxes or ethylene copolymer waxes, as obtainable, for example, by free-radical polymerization of ethylene or free-radical copolymerization of ethylene with, for example, (meth) acrylic acid or by Ziegler-Natta catalysis. Furthermore, polyisobutylene waxes may be mentioned. Furthermore, be mentioned paraffin mixtures; including Gemi ⁇ are specific understanding of hydrocarbons 12 or more carbon atoms have auf ⁇ and usually have a melting point in the range of 25 to 45 0 C. Such paraffin mixtures can be obtained, for example, in refineries or crackers and are known to the person skilled in the art as slack wax and Sasol waxes. Another example of synthetic waxes are montan ester waxes.
  • liquid triglycerides are mentioned at room temperature, for example fish oil, cattle claw oil, olive oil, cottonseed oil, castor oil, sunflower oil and peanut oil.
  • synthetic oils examples include white oil, paraffin oil, functionalized paraffins such as chlorinated or sulfochlorinated paraffins or polyalkylene glycols such as polyethylene glycol.
  • solid native triglycerides such as, for example, lanolin, shellac wax and mixtures thereof, are mentioned at room temperature.
  • Examples of synthetic polymers include maleic anhydride- ⁇ -olefin copolymers as disclosed in EP-A 0 412 389, furthermore copolymers obtainable by copolymerization of at least one ethylenically unsaturated dicarboxylic acid anhydride derived from at least one dicarboxylic acid having 4 to 8 C atoms, at least one oligomer of branched or unbranched C 3 -C 10 -alkene , where at least one oligomer has an average molecular weight M n in the range from 300 to 5,000 g / mol or by oligomerization of at least 3 equivalents of C 3 - Cio-alkene is available, and hydrolysis of the anhydride groups, wherein one can react before hydrolysis optionally with at least one simple to 100-fold ethoxylated vorzugs ⁇ linear C 1 -C 30 alkanol.
  • a hydrophobic substance is at least one native triglyceride.
  • an amphiphilic substance is at least one synthetic polymer.
  • a combination of at least one native or liquid native triglyceride at room temperature and a paraffin mixture having a melting point in the range from 25 to 40 ° C. are used.
  • the quantitative ratio is not critical per se; suitable ratios are, for example, weight ratios of native triglyceride: paraffin mixture in the range from 10: 1 to 1:10.
  • formulations according to the invention comprise one or more emulsifiers which may be anionic, cationic, nonionic or zwitterionic.
  • Suitable nonionic emulsifiers are, for example, ethoxylated mono-, di- and tri-alkylphenols (degree of ethoxylation: from 3 to 50, alkyl radical: C 4 -C 12 ) and ethoxylated fatty alcohols (degree of ethoxylation: from 3 to 80, alkyl radical: C 8 -C 36 ).
  • ethoxylated mono-, di- and tri-alkylphenols degree of ethoxylation: from 3 to 50, alkyl radical: C 4 -C 12
  • ethoxylated fatty alcohols degree of ethoxylation: from 3 to 80, alkyl radical: C 8 -C 36
  • Lutensol ® brands of BASF Aktiengesellschaft are the Lutensol ® brands of BASF Aktiengesellschaft.
  • Suitable anionic emulsifiers are, for example, alkali metal and ammonium salts of alkyl sulfates (alkyl radical: C 8 to C 12 ), of sulfuric monoesters of ethoxylated alkanols (degree of ethoxylation: from 4 to 30, alkyl radical: C 12 -C 18 ) and ethoxylated alkylphenols (degree of ethoxylation: from 3 to 50, Alkyl radical: C 4 -C 12 ), of alkylsulfonic acids (alkyl radical: C 12 -C 18 ), of alkylarylsulfonic acids (alkyl radical: C 9 -C 18 ), and of sulfosuccinates, such as, for example, succinic acid mono- and diesters.
  • alkyl sulfates alkyl radical: C 8 to C 12
  • sulfuric monoesters of ethoxylated alkanols degree of ethoxylation: from
  • Suitable cationic emulsifiers are generally a C 6 -C 18 -alkyl, aralkyl or heterocyclic radical-containing primary, secondary, tertiary or quaternary ammonium salts, alkanolammonium salts, pyridinium salts, imidazolinium salts, oxazolinium salts, morpholinium salts, thiazolinium salts and salts of amine oxides, Quinolinium salts, isoquinolinium salts, tropylium salts, sulfonium salts and phosphonium salts.
  • Examples include dodecylammonium acetate or the corresponding hydrochloride, the chlorides or acetates of the various 2- (N, N, N-trimethylammonium) ethylparaffinklaer, ⁇ / -Cetylpyridiniumchlorid, ⁇ / -Laurylpyridiniumsulfat and ⁇ / -Cetyl- ⁇ /, / , ⁇ / -trimethylammonium bromide, ⁇ / -dodecyl- / V, ⁇ /, / V-trimethylammonium bromide, ⁇ /, ⁇ / -istearyl- ⁇ /, ⁇ / -dimethylammonium chloride and the gemini surfactant ⁇ /, / V- (lauryldimethyl ) ethylendiamindibromid.
  • emulsifiers are N-acylated amino acid derivatives beispiels ⁇ the formula III
  • R 6 is C 1 -C 4 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl; especially methyl;
  • R 7 is hydrogen, C 1 -C 4 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl, in particular methyl;
  • C 6 -C 14 aryl for example phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-Phe - Nanthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, more preferably phenyl.
  • the group CO-R 8 is preferably derived from saturated or unsaturated fatty acids.
  • Saturated fatty carboxylic acids having C 9 -C 2 are to be understood O-alkyl groups, which may be linear or branched, substituted or unsubstituted.
  • R 8 may be, for example: n-nonyl, n-decyl, n-dodecyl, n-tetradecyl, n-pentadecyl, n-octadecyl, n-eicosyl.
  • CO-R 8 can be derived from an unsaturated fatty acid having 9 to 20 C atoms and one to 5 CC double bonds, wherein the CC double bonds can be, for example, isolated or allylic, for example the acyl radical of linoleic acid, the linolenic acid, and most preferably the oleic acid.
  • all or at least one certain proportion, for example one third or one-half, of the carboxyl groups in N-acylated amino acid derivatives of the formula IV used as emulsifiers is neutralized.
  • neutralization for example, basic salts such as hydroxides or carbonates of alkali metals such as Na or K.
  • alkylamines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, and very particularly alkanolamines such as for example, ethanolamine, diethanolamine, triethanolamine, N-methyl-ethanolamine, N-methyldiethanolamine or N- (n-butyl) -diethanolamine.
  • Exemplary representatives of compounds of the formula III are N-oleylsarcosine, N-stearylsarcosine, N-lauroylsarcosine and N-isononanoylsarcosine, and also the respective ethanolammonium salts, diethanolammonium salts and N-methyldiethanolammonium salts.
  • emulsifiers are those of the general formula IV
  • R 9 , R 10 are the same or preferably different and selected from hydrogen
  • C 1 -C 30 -alkyl branched or unbranched, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isobutyl Pentyl, sec-pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, iso-heptyl, n-octyl, n-nonyl, n- Decyl, n-undecyl, n-
  • Phenanthryl and 9-phenanthryl preferably phenyl, 1-naphthyl and 2-naphthyl, more preferably phenyl;
  • R 11 is selected from C 1 -C 4 -alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl and especially hydrogen;
  • R 12 , R 13 is the same or preferably different and selected from G- ⁇ -C 27 -alkyl, such as
  • R 11 has two C atoms more than R 12 ;
  • R 14 is selected from C 1 -C 4 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, phenyl, ortho-tolyl, meta-tolyl, para-tolyl and especially hydrogen.
  • R 9 and R 10 are hydrogen and the other is selected from C 1 -C 30 -alkyl.
  • a mixture of a plurality of emulsifiers for example of the formula IV, which may differ, for example, in that in the first compound the
  • R 9 is hydrogen and R 10 is selected from CrC 30 alkyl and in thetician ⁇ th R 10 is hydrogen and R 9 is selected from CrC 3 o-alkyl.
  • all or at least one certain portion, for example one third or one-half, of the sulfonyl groups is neutralized in emulsifiers of the formula VI.
  • Suitable for neutralization are, for example, basic salts such as hydroxides or carbonates of the alkali metals such as Na or K.
  • Further suitable for neutralization are ammonia, alkylamines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethylenediamine and most particularly Alkanolamines such as ethanolamine, diethanolamine, triethanolamine, N-methyl-ethanolamine, N-methyldiethanolamine or N- (n-butyl) -diethanolamine.
  • Formulations according to the invention may contain mixtures of different emulsifiers instead of purified emulsifiers, for example of formula IV.
  • esterification it is possible for esterification to add the mixture known as oxo oil 135 or oxo dip oil 135 (WO 01/68584) and to use the mixture of esters obtainable as emulsifier.
  • emulsifiers present in formulations according to the invention may contain up to 40% by weight, preferably up to 20% by weight, based on emulsifier, of at least one alcohol of the formula VI
  • emulsifiers present in dispersions of the invention may contain up to 40% by weight, particularly preferably up to 20% by weight, of mixtures which comprise at least one alcohol of the general formula X; oxo oil 135 and oxo oil 13 may be mentioned as examples of such mixtures.
  • formulations according to the invention comprise a combination of two emulsifiers, of which one emulsifier is selected from emulsifiers of the general formula III and IV and the other of ethoxylated fatty alcohols having a degree of ethoxylation: 3 to 80; Alkyl radical: nC 8 -C 36 .
  • formulations according to the invention contain ⁇ ) 50 to 100% by weight, preferably 60 to 90% by weight of copolymer of the invention, ⁇ ) 0 to 50% by weight, preferably 10 to 40% by weight hydrophobic substance selected from
  • Oils, waxes and synthetic polymers ⁇ ) 0 to 20 wt .-%, preferably 1 to 15 wt .-% emulsifier,
  • wt .-% in each case based on the solids content of the entire inventive formulation.
  • the remainder of the formulation according to the invention is preferably water.
  • Formulations according to the invention allow a particularly simple metering of copolymers according to the invention. Inventive formulations are further characterized by good performance properties such as storage stability.
  • Formulations according to the invention can be prepared by methods known per se, for example by mixing the individual components water, ⁇ ), optionally ⁇ ) and optionally ⁇ ).
  • the order of addition of the individual components water, ⁇ ), optionally ⁇ ) and optionally ⁇ ) is not critical.
  • the mixing can take place, for example, by simply stirring the components together, for example in a stirred tank, for example using a mixer or an Ultra Thurax stirrer.
  • further homogenization is carried out, e.g. with a
  • the characterization of copolymers according to the invention was carried out with the aid of the preparative ultracentrifuge and subsequent size exclusion chromatography (SEC), the serum and the dispersed phase being separated.
  • the serum was diluted in distilled water with 0.08 mol / l tris (hydroxymethyl) aminomethane buffer at pH 7 with the addition of 0.15 mol / l Cl ions (as NaCl) and 0.001 mol / l NaN 3 ,
  • the calibration was carried out with a widely distributed Na-PAA mixture 23250/158/2 (sodium salt of polyacrylic acid) whose integral molecular weight distribution curve had been determined by SEC laser light scattering, according to the calibration method of MJR Cantow et al. (J. Polym., Vol. A-1, 5 (1967) 1391-1394), but without the concentration correction proposed therein.
  • the glass transition temperature T g was calculated according to the Fox equation.
  • Feed 3 147 g of 2-ethylhexyl acrylate 70 g of water
  • Feed 4 10 g of sodium peroxodisulfate 160 g of water
  • Copolyme invention CP1.1 was obtained as an aqueous dispersion.
  • the aqueous dispersion of CP1.1 thus prepared had a solids content of 42.9% and a pH of 5.0.
  • Feed 2 7.8 g of sodium peroxodisulfate 124 g of water
  • feed 1 was added continuously at the same time within 3 hours and feed 2 within 3.5 hours.
  • the resulting reaction mixture wur ⁇ de 90 minutes at 80 0 C stirred.
  • the mixture was then cooled to room temperature and the resulting reaction mixture was admixed with a solution of 16.5 g of NaOH in 80 g of water.
  • Copolymers of the invention CP1.2 were obtained as an aqueous dispersion.
  • the aqueous dispersion of CP1.2 thus prepared had a solids content of 43.8% and a pH of 5.3.
  • Feed 1 36 g of methacrylic acid 140 g of water
  • Feed 3 143 g of 2-ethylhexylacryate at 65 g of water
  • Feed 4 10 g of sodium peroxodisulfate 160 g of water
  • Copolyester CP1.3 according to the invention was obtained as an aqueous dispersion.
  • the aqueous dispersion of CP1.3 thus prepared had a solids content of 41.6% and a pH of 6.1.
  • Feed 3 20 g of C 13 -oxo alcohol ethoxylate (7 ethylene oxide / mol)
  • a 2 l polymerization vessel was charged with 650 g of an aqueous dispersion of copolymer CP1.1 and admixed with the inlets 1 to 3 at room temperature within 1 hour. The reaction mixture was then stirred for 1 hour at room temperature.
  • the aqueous formulation 2.1 thus prepared had a solids content of 40.0% by weight and a pH of 5.2.
  • a 2 l polymerization vessel was charged with 650 g of an aqueous dispersion of copolymer CP1.1 and admixed with the inlets 1 to 2 at room temperature within 1 hour. The reaction mixture was then stirred for 1 hour at room temperature.
  • the aqueous formulation 2.2 thus prepared had a solids content of 52.0% and a pH of 4.7.
  • the data in% by weight are based on the shaved weight, unless stated otherwise.
  • the washed leathers were dried and dressed and milled for 15 hours.
  • the leather 3.1 according to the invention was obtained. and 3.2.
  • the leathers 3.1 and 3.2 according to the invention had excellent fullness and softness and feel with excellent through-dyeing of the fibers.
  • the leathers show a pronounced hydrophobization without having been treated with water-repellents based on silicone compounds, wherein the hydrophobization according to the invention can even exceed the effect of silicone oils.
  • Ci 6 H 33 O- (CH 2 CH 2 O) 7 -OH added.
  • the resulting emulsion was then passed through a split homogenizer. A finely divided, stable emulsion was obtained.

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Abstract

La présente invention concerne des copolymères qui sont préparés par copolymérisation en au moins deux étapes. L'invention se caractérise par les étapes suivantes : (A) préparation d'au moins un (co)polymère, à partir d'un monomère ou d'un mélange de comonomères comprenant (a1) 80 à 100 % en poids d'au moins un acide carboxylique éthyléniquement insaturé, (a2) 0 à 20 % en poids d'au moins un alkylester en C<SUB>1</SUB>-C<SUB>22</SUB> d'au moins un acide carboxylique éthyléniquement insaturé, (a3) 0 à 10 % en poids d'au moins un autre composé éthyléniquement insaturé, les pourcentages en poids se référant à la quantité totale de comonomères de l'étape concernée ; puis (B) conversion du (co)polymère ainsi obtenu, avec un autre comonomère ou un autre mélange de comonomères comprenant (b1) 0 à 30 % en poids d'au moins un acide carboxylique éthyléniquement insaturé, (b2) 70 à 100 % en poids d'au moins un alkylester en C<SUB>1</SUB>-C<SUB>22</SUB> d'au moins un acide carboxylique éthyléniquement insaturé, (b3) 0 à 10 % en poids d'au moins un autre composé éthyléniquement insaturé, les pourcentages en poids se référant à la quantité totale de comonomères de l'autre étape concernée.
EP05778453A 2004-08-05 2005-07-30 Copolymeres, leur preparation et leur utilisation Withdrawn EP1776391A1 (fr)

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DE200410038217 DE102004038217A1 (de) 2004-08-05 2004-08-05 Copolymerisate, ihre Herstellung und Verwendung
PCT/EP2005/008278 WO2006015745A1 (fr) 2004-08-05 2005-07-30 Copolymeres, leur preparation et leur utilisation

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WO2008022918A2 (fr) * 2006-08-23 2008-02-28 Basf Se Composés et leur utilisation pour la fabrication de cuir et en tant qu'agents de dispersion
PT2190913E (pt) 2007-09-03 2015-10-20 Basf Se Processo para a produção de formulações aquosas, formulações aquosas e a sua utilização
EP2190891A1 (fr) * 2007-09-03 2010-06-02 Basf Se Procédé de production de formulations aqueuses, formulations aqueuses et leur utilisation

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US4810763A (en) * 1987-12-23 1989-03-07 Avery International Corporation Suspension polymerization in an organic medium
US4944888A (en) * 1987-12-23 1990-07-31 Avery International Corporation Suspension polymerization in an organic medium
US6376600B1 (en) * 1998-07-24 2002-04-23 Rohm And Haas Company Aqueous composition
EP1335029A1 (fr) * 2002-02-08 2003-08-13 Basf Aktiengesellschaft Procédé de préparation de cuir et de fourrure

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BRPI0514114A (pt) 2008-05-27
US20080201864A1 (en) 2008-08-28

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