EP0349935A2 - Solutions aqueuses de resines polyamide-amine-epichlorhydrine, leur procédé de préparation et leur utilisation - Google Patents
Solutions aqueuses de resines polyamide-amine-epichlorhydrine, leur procédé de préparation et leur utilisation Download PDFInfo
- Publication number
- EP0349935A2 EP0349935A2 EP89112049A EP89112049A EP0349935A2 EP 0349935 A2 EP0349935 A2 EP 0349935A2 EP 89112049 A EP89112049 A EP 89112049A EP 89112049 A EP89112049 A EP 89112049A EP 0349935 A2 EP0349935 A2 EP 0349935A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- resin
- acid
- epichlorohydrin
- polyamidoamine
- resin solution
- 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.)
- Granted
Links
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
- D21H17/55—Polyamides; Polyaminoamides; Polyester-amides
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/18—Reinforcing agents
- D21H21/20—Wet strength agents
Definitions
- US Pat. No. 3,352,833 describes, inter alia, an alkaline aftertreatment of polyamidoamine-epichlorohydrin resins for reactivating the wet strength activity.
- the acidified resin solutions are then reacted with 0.25 to 2.5 equivalents of base per equivalent of acid in aqueous solution.
- the base is added before using the resin for papermaking, and the resin solution is left to age for four hours and then used immediately.
- the reworking of the alkaline aftertreatment specified in this US patent shows that this does not result in resin solutions which are sufficiently stable in storage and / or low in chlorine (cf. the further comparative experiments below).
- the present invention now relates to a storage-stable, aqueous resin solution with a pH of at most 7, containing as resin a water-dilutable, preferably water-soluble polyamidoamine-epichlorohydrin resin (A) obtained by converting a water-dilutable, preferably water-soluble, basic polyamidoamine (B) , consisting of an acid component (B1) and an amine component (B2), with epichlorohydrin (C), the content of organically bound chlorine in the resin (A) being at most 4% by weight and the component (B2) - if the acid component (B1) is an aliphatic or aromatic carboxylic acid or its functional derivatives, optionally in admixture with an amino carboxylic acid or its lactams - consists of a mixture of polyamines and alkanol monoamines.
- A water-dilutable, preferably water-soluble polyamidoamine-epichlorohydrin resin
- A water-dilutable
- the invention relates to a process for the preparation of these resin solutions and their use.
- stable in storage is intended here to mean that no noticeable gelation or precipitation occurs during storage for at least three months at room temperature (or for at least 10 days at 50 ° C.).
- solution is also intended to include a colloidal solution.
- the pH of the resin solution according to the invention is preferably between 1.5 and 5.
- the viscosity of a 12.5% solution at 25 ° C. is generally about 10 to 200, preferably 15 to 80 mPa.s.
- the content of resin (A) in the solution according to the invention is generally between 8 and 25% by weight, preferably 10 and 15% by weight, based on the solution.
- this resin solution contains small amounts of inorganic substances (from the base treatment and the subsequent neutralization) and optionally up to 0.5% by weight, preferably 0.05 to 0.2% by weight, of antifungal agents, such as sorbic acid or Potassium sorbate and optionally other additives, such as, for example Defoaming agent.
- antifungal agents such as sorbic acid or Potassium sorbate
- other additives such as, for example Defoaming agent.
- the resin (A) generally has an average molecular weight M n of at least 500, preferably of at least 1000 and in particular of 1000 to 500,000.
- the content of organically bound chlorine is generally between 0.1 and 4, preferably between 1 and 4 and in particular between 1 and 3% by weight. In a 12.5% resin solution, this chlorine content does not exceed 0.5% by weight and is generally between 0.0125 and 0.5, preferably between 0.125 and 0.5 and in particular between 0.125 to 0.375% by weight, based on the solution.
- the amount of units in (A) derived from the epichlorohydrin is generally 20 to 50% by weight, preferably 30 to 40% by weight, based on (A).
- the process according to the invention for the preparation of the resin solutions described above is characterized in that water-soluble, basic polyamidoamines (B) are reacted with epichlorohydrin (C) in a ratio of 0.6 to 2 moles per mole of basic amino groups of the polyamidoamine (B) in an aqueous system brings, and then, optionally after prior acidification of the reaction system, with as much a base (D), generally 0.1 to 1.0 mol, preferably 0.1 to 0.6 mol per mol of epichlorohydrin used, at 25 to 95 ° C converts that the pH is greater than 8, then adjusts the pH to at most 7 by adding acid.
- a base generally 0.1 to 1.0 mol, preferably 0.1 to 0.6 mol per mol of epichlorohydrin used, at 25 to 95 ° C converts that the pH is greater than 8, then adjusts the pH to at most 7 by adding acid.
- the water-soluble polyamidoamine (B) generally has an average molecular weight M n (determined via the carboxyl end groups) of at least 500, preferably at least 1000 and in particular 2000 to 20,000; the amine number is usually between 200 and 400, preferably between 250 and 350 mg KOH / g and the acid number between 0 and 50, preferably 10 and 30 mg KOH / g.
- Polyamidoamines (B) which meet the conditions according to the invention are, for example, in DE-AS 1,777,824, GB-PS 865,727, US-PS 4,075,177 and 4,336,835, DE-OS 3,323,732 and EP -OS 31 899 described, to which reference is made here.
- the corresponding products according to DE-OS 3,323,732 are preferred insofar as they come under the present framework.
- Polyamidoamines (B) of this type are generally obtained by reacting the acid component (B1), such as dicarboxylic acids or their functional derivatives, and ⁇ -aminocarboxylic acids or their lactams with the amine component (B2), such as polyamines, these being present in a mixture with alkanolmonoamines if ( B1) meets the conditions mentioned above.
- These polyamines contain at least two primary amino groups and preferably at least one secondary and / or tertiary amino group.
- the quantity ratio of the components is to be chosen so that in the resulting polyamidoamine (B) there is still a sufficient number of basic (ie reactive with epichlorohydrin (C)) amino groups, no gelation occurs during the reaction and the molecular weight of (A) in the specified range.
- Reaction products of type 1) using diethylene triamine, triethylene tetramine and tetraethylene pentamine as the polyamine and 2-aminoethanol as the alkanol monoamine are particularly preferred.
- Examples of polyamines b1) and c1) are those of the formula (I) considered in the p is zero or an integer from 1 to 6, preferably 1 to 4,
- R1 is a divalent, preferably non-aromatic hydrocarbon radical having 2 to 18 carbon atoms, preferably a branched or unbranched alkylene radical having 2 to 10 carbon atoms, in particular having 2 to 6 carbon atoms, or a cycloalykylene radical having 5 to 12 carbon atoms, preferably 6 to 10 carbon atoms, or an aralkylene radical having 7 to 12 carbon atoms, preferably 8 to 10 carbon atoms and R2, R 2 ' independently of one another for H or one of the two radicals for stand in which R1 has the same meaning as above and R3, R4 are either independently of one another H, (C1-C20) alkyl, preferably (C1-C6) alkyl, where these alkyl radicals can also carry hydroxyl groups.
- polyamines b1) are called methyl bis (3-aminopropyl) amine, ethyl bis (3-aminopropyl) amine, N- (3-aminopropyl) tetramethylene diamine, N, N'-bis (3-aminopropyl) tetramethylene diamine, Polyalkylene polyamines such as di-propylene- (1,2) -triamine, bis- (3-aminopropyl) -amine, tripropylene- (1,2) -tetramine and especially diethylene triamine, triethylene tetramine and tetraethylene pentamine.
- Polyamines c1) are, for example: ethylenediamine, propylenediamine, 1-amino-3-methylamino-propane, 2-methylpentamethylene diamine, pentanethylene diamine, hexamethylene diamine, trimethyl hexamethylene diamine, neopentyl diamine, octamethylene diamine, dioxadodecane diamine, cyclialiphatic diamines such as 1,2-, 1,3- or 1,4-cyclohexane diamine; 4,4'-methylene-bis-cyclohexylamine, isophoronediamine, menthandiamine, 4,4'-diamino-3,3'-dimethyl-di-cyclohexylmethane, 3-aminomethyl-1- (3-aminopropyl-1-methyl) -4 -methylcyclohexane, N-methylethylenediamine, N-aminoethylpiperazine, 1,3-bis-amin
- alkanol monoamines are those of the formula H2N-R1-OH (II) suitable in which R1 has the above meaning, such as 2-aminoethanol, 1-amino-2-propanol, 3-amino-1-propanol, 2-amino-1-butanol, 4-amino-1-butanol, 5-amino -1-pentanol, 6-amino-1-hexanol and their isomers, the hydrocarbon radical of which is branched or which carry the amino group and / or the hydroxyl group on a primary or secondary carbon atom; furthermore those which are derived from cyclic hydrocarbon radicals, preferably having 5-7 carbon atoms.
- the molar amount of dicarboxylic acid or its functional derivatives to polyamine / alkanol monoamine is such that the ratio of carboxyl groups to the sum of primary NH2 groups 1: (0.8-1.4), preferably 1: (0, 95-1.1).
- the ratio of their molar amounts is 0.6: 0.4 to 0.99: 0.01, preferably 0.8: 0.2 to 0.95: 0.05.
- the polyamidoamines (B) can be prepared in the customary manner, for example by heating the for several hours corresponding components with the exclusion of oxygen at temperatures of 125 to 250 ° C, preferably from 140 to 180 ° C, first under ordinary pressure and then under reduced pressure, with a small amount of hydrazine hydrate or hydrazides can be added to avoid the darkening of the polyamides.
- the reaction time depends on the temperatures and pressures used and is generally between 4 and 10 hours.
- dichlorohydrin (1,3-dichloro-2-hydroxypropane) can optionally also be used.
- Bases (D) which can be used include: alkali metal hydroxides, preferably sodium and potassium hydroxide, carbonates, bicarbonates, alkaline earth metal hydroxides, such as calcium hydroxide, furthermore benzyltrimethylammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide or corresponding mixtures.
- the reaction products can be prepared by the process according to the invention in such a way that the polyamidoamines (B) and epichlorohydrin (C) are in a first reaction step at a concentration of the reactants of about 25 to 50%, preferably 35 to 45% and at one Temperature between 25 and 95 ° C, preferably 40 to 70 ° C, until it can react until the viscosity of a 40% solution (determined at 25 ° C) is about 100 to 600, preferably 200 to 400 mPa.s.
- This solution is then set in a second reaction step with an aqueous solution of a base (D) which is used in an amount of generally 0.1 to 1.0, preferably 0.1 to 0.6, mol per mol of epichlorohydrin (C) is contained, at a concentration of the reactants of 10 to 40%, preferably 15 to 25%, and a temperature between 25 to 95 ° C, preferably 40 to 70 ° C, until the viscosity a 12.5% solution (determined at 25 ° C.) is 10-200 mPa.s, preferably 15 to 80 mPa.s.
- the pH in this second reaction step is greater than 8, preferably between 9 and 12.
- the mixture is expediently added to the mixture in order to terminate the action and to stabilize the self-crosslinking reaction products, so much acid or acid derivatives that the pH the aqueous solution is 1 to 7, preferably between 1.5 and 5, and adjusts the solids content of the reaction solution to 8 to 25% by weight by dilution with water.
- acid can be added to the solution during or after the reaction of polyamidoamine (B) and epichlorohydrin (C) and the pH can be adjusted to less than 7, preferably 1.5 and 5.
- Sufficient base (D) is then added to this acidic reaction mixture such that the pH is greater than 8, preferably between 9 and 12, and this system is then used for a period of 0.5 to 8 hours, preferably 1 to 4 hours at a temperature of 25 to 95 ° C, preferably 40 to 70 ° C.
- Halogen-free acids such as sulfuric, phosphoric or acetic acid are particularly suitable as acids and corresponding anhydrides or acidic salts as acid derivatives.
- the amount of epichlorohydrin (C) is generally 0.6 to 2 mol, preferably 1.0 to 1.4 mol, per mol of basic amino groups (primary, secondary or tertiary) in the polyamidoamine (B) and the amount of base (D) 0.1 to 1.0 mol, preferably 0.1 to 0.6 mol, per mol of epichlorohydrin used.
- the resins or resin solutions according to the invention have a considerably lower level than the previously known reaction products of polyamidoamine and epichlorohydrin organically bound chlorine content and are therefore ideally suited to significantly reduce the organic chlorine content of wastewater, including paper mills.
- the reaction products which have hitherto been used to improve the wet strength effectiveness of paper do not possess this valuable property to the same extent. Due to the high storage stability of the resin solutions according to the invention, their wet strength effectiveness remains constant even after months of storage.
- the wet strength of paper - including paper made from unbleached cellulose - can be outstandingly improved. In some cases, depending on the type of paper or as desired, it is also possible to increase the absorbency. It is noteworthy that the reaction products practically do not affect the whiteness of paper made from bleached pulp. It should also be mentioned that the speed at which the reaction products to be used according to the invention crosslink on the paper or in the pulp is high and that the reaction products are also used as retention aids for fillers used in papermaking, drainage aids to improve the papermaking speed and flocculants to remove fine particles Particles from dirty water, for example industrial waste water, can be used.
- the resins in question in the form of aqueous solutions to the aqueous suspension of the paper raw material before processing into paper.
- the amounts of resin required to achieve the desired wet strength can be determined by Determine preliminary tests without difficulty.
- the polyamidoamine was diluted with 570 g of water.
- the solution had a solids content of 59.8% (1 g, 1 hour, 125 ° C.) and a viscosity at 25 ° C. of 1174 mPa.s.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paper (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Polyamides (AREA)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT89112049T ATE90405T1 (de) | 1988-07-02 | 1989-07-01 | Waessrige loesungen von polyamidoamin-epichlorhyrin-harzen, verfahren zu ihrer herstellung und ihre verwendung. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3822490 | 1988-07-02 | ||
DE3822490A DE3822490A1 (de) | 1988-07-02 | 1988-07-02 | Waessrige loesungen von polyamidoamin-epichlorhyrin-harzen, verfahren zu ihrer herstellung und ihre verwendung |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0349935A2 true EP0349935A2 (fr) | 1990-01-10 |
EP0349935A3 EP0349935A3 (fr) | 1991-05-08 |
EP0349935B1 EP0349935B1 (fr) | 1993-06-09 |
Family
ID=6357862
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP89112049A Expired - Lifetime EP0349935B1 (fr) | 1988-07-02 | 1989-07-01 | Solutions aqueuses de resines polyamide-amine-epichlorhydrine, leur procédé de préparation et leur utilisation |
Country Status (5)
Country | Link |
---|---|
US (1) | US5019606A (fr) |
EP (1) | EP0349935B1 (fr) |
AT (1) | ATE90405T1 (fr) |
DE (2) | DE3822490A1 (fr) |
ES (1) | ES2058408T3 (fr) |
Cited By (20)
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EP0512423A2 (fr) * | 1991-05-06 | 1992-11-11 | Hoechst Aktiengesellschaft | Solutions aqueuses de résines polyamidoamine cationiques |
US5171795A (en) * | 1990-08-01 | 1992-12-15 | Hercules Incorporated | Process for the production of improved polyaminopolyamide epichlorohydrin resins |
WO1992022601A1 (fr) * | 1991-06-19 | 1992-12-23 | Akzo N.V. | Resines a base d'epihalohydrine a teneur reduite en halogene |
WO1993003222A1 (fr) * | 1991-08-05 | 1993-02-18 | Henkel Corporation | Composition de resine de resistance a l'etat humide et procede de preparation |
US5470742A (en) * | 1991-04-24 | 1995-11-28 | Hercules Incorporated | Dehalogenation of organohalogen-containing compounds |
EP0703265A1 (fr) | 1994-07-22 | 1996-03-27 | Hoechst Aktiengesellschaft | Hydrogels hydrophiles à capacité de gonflement élevée |
WO1999009252A1 (fr) * | 1997-08-13 | 1999-02-25 | Fort James Corporation | Formulations de resines thermodurcissables resistant au mouille et polymeres de polyaminamide appropries pour l'emploi dans la fabrication de produits en papier |
US5972691A (en) * | 1995-06-07 | 1999-10-26 | Hercules Incorporated | Dehalogenation of polyamine, neutral curing wet strength resins |
US6107432A (en) * | 1997-05-28 | 2000-08-22 | Basf Ag | Water-swellable, hydrophilic polymer compositions |
US6429267B1 (en) | 1997-12-31 | 2002-08-06 | Hercules Incorporated | Process to reduce the AOX level of wet strength resins by treatment with base |
US6472478B1 (en) | 1998-02-21 | 2002-10-29 | Basf Aktiengesellschaft | Process for crosslinking hydrogels with bis- and poly-2- oxazolidinones |
US6503979B1 (en) | 1998-02-26 | 2003-01-07 | Basf Aktiengesellschaft | Method for cross-linking hydrogels with bis- and poly-2-oxazolidinones |
US6559239B1 (en) | 1998-11-26 | 2003-05-06 | Basf Aktiengesellschaft | Method for the secondary cross-linking of hydrogels with N-acyl-2-oxazolidinones |
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US7175740B2 (en) | 1999-06-11 | 2007-02-13 | Hercules Incorporated | Reduced by product polyamine-epihalohydrin resins |
US7183360B2 (en) | 2001-10-05 | 2007-02-27 | Basf Aktiengesellschaft | Method for crosslinking hydrogels with morpholine-2,3-diones |
US7303652B2 (en) | 2000-12-09 | 2007-12-04 | Hercules Incorporated | Reduced byproduct high solids polyamine-epihalohydrin compositions |
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US7655733B2 (en) | 2004-08-04 | 2010-02-02 | Basf Aktiengesellschaft | Postcrosslinking of water absorbing polymers with cyclic carbamates and/or cyclic ureas |
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US5256727A (en) * | 1992-04-30 | 1993-10-26 | Georgia-Pacific Resins, Inc. | Resins with reduced epichlorohydrin hydrolyzates |
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US5567798A (en) * | 1994-09-12 | 1996-10-22 | Georgia-Pacific Resins, Inc. | Repulpable wet strength resins for paper and paperboard |
US5614597A (en) | 1994-12-14 | 1997-03-25 | Hercules Incorporated | Wet strength resins having reduced levels of organic halogen by-products |
JPH08302006A (ja) * | 1995-05-09 | 1996-11-19 | Mitsubishi Gas Chem Co Inc | 低塩素変性ポリアミンおよび水系エポキシ樹脂硬化剤 |
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US5786429A (en) * | 1996-04-18 | 1998-07-28 | Hercules Incorporated | Highly branched polyamidoamines and their preparation |
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EP0131200A2 (fr) * | 1983-07-01 | 1985-01-16 | Hoechst Aktiengesellschaft | Produits réactionnels solubles dans l'eau, qui sont essentiellement exempts de liaisons d'ester, à partir d'épihalohydrine et de polyamidoamines basiques qui sont solubles dans l'eau, procédé pour leur préparation et leur utilisation |
EP0282862A2 (fr) * | 1987-03-17 | 1988-09-21 | Bayer Ag | Composés contenant de l'azote, solubles dans l'eau |
EP0332967A2 (fr) * | 1988-03-16 | 1989-09-20 | Bayer Ag | Résine polyamido-amine |
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FR2292729A1 (fr) * | 1974-11-29 | 1976-06-25 | Protex Manuf Prod Chimiq | Procede de preparation de resines cathioniques thermodurcissables, resines obtenues suivant ce procede et leurs applications, notamment pour l'amelioration de la resistance a l'etat humide du papier |
JPS54159496A (en) * | 1978-06-07 | 1979-12-17 | Sumitomo Chem Co Ltd | Preparation of aqueous solution of cationic thermosetting resin |
DE2949870A1 (de) * | 1979-12-12 | 1981-06-19 | Hoechst Ag, 6230 Frankfurt | Kondensationsprodukte zur erhoehung der nassfestigkeit von papier |
DE3003648A1 (de) * | 1980-02-01 | 1981-08-06 | Basf Ag, 6700 Ludwigshafen | Verfahren zur zerstellung von wasserloeslichen, stickstoffhaltigen kondensationsprodukten und deren verwendung bei der papierherstellung |
DE3135830A1 (de) * | 1981-09-10 | 1983-03-24 | Basf Ag, 6700 Ludwigshafen | Verfahren zur herstellung von wasserloeslichen, stickstoffhaltigen kondensationsprodukten und deren verwendung bei der papierherstellung |
DD218276A1 (de) * | 1983-07-21 | 1985-02-06 | Univ Leipzig | Verfahren zum herstellen monoklonaler antikoerper fuer ein t-zell-antigen |
DD223456A1 (de) * | 1984-01-18 | 1985-06-12 | Leuna Werke Veb | Verfahren zur herstellung von epoxidharzen mit niedrigem chlorgehalt |
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GB8613652D0 (en) * | 1986-06-05 | 1986-07-09 | Grace W R Ab | Compositions for sizing paper |
US4870119A (en) * | 1986-11-24 | 1989-09-26 | Sandoz Ltd. | Water-soluble polyamides containing aromatic groups |
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- 1988-07-02 DE DE3822490A patent/DE3822490A1/de not_active Withdrawn
-
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- 1989-06-30 US US07/374,467 patent/US5019606A/en not_active Expired - Fee Related
- 1989-07-01 ES ES89112049T patent/ES2058408T3/es not_active Expired - Lifetime
- 1989-07-01 AT AT89112049T patent/ATE90405T1/de not_active IP Right Cessation
- 1989-07-01 DE DE8989112049T patent/DE58904602D1/de not_active Expired - Fee Related
- 1989-07-01 EP EP89112049A patent/EP0349935B1/fr not_active Expired - Lifetime
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EP0131200A2 (fr) * | 1983-07-01 | 1985-01-16 | Hoechst Aktiengesellschaft | Produits réactionnels solubles dans l'eau, qui sont essentiellement exempts de liaisons d'ester, à partir d'épihalohydrine et de polyamidoamines basiques qui sont solubles dans l'eau, procédé pour leur préparation et leur utilisation |
EP0282862A2 (fr) * | 1987-03-17 | 1988-09-21 | Bayer Ag | Composés contenant de l'azote, solubles dans l'eau |
EP0332967A2 (fr) * | 1988-03-16 | 1989-09-20 | Bayer Ag | Résine polyamido-amine |
Cited By (26)
Publication number | Priority date | Publication date | Assignee | Title |
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US5171795A (en) * | 1990-08-01 | 1992-12-15 | Hercules Incorporated | Process for the production of improved polyaminopolyamide epichlorohydrin resins |
US5470742A (en) * | 1991-04-24 | 1995-11-28 | Hercules Incorporated | Dehalogenation of organohalogen-containing compounds |
US5843763A (en) * | 1991-04-24 | 1998-12-01 | Hercules Incorporated | Dehalogenation of organohalogen-containing compounds |
US5871616A (en) * | 1991-04-24 | 1999-02-16 | Hercules Incorporated | Dehalogenation of organohalogen-containing compounds |
EP0512423A2 (fr) * | 1991-05-06 | 1992-11-11 | Hoechst Aktiengesellschaft | Solutions aqueuses de résines polyamidoamine cationiques |
EP0512423A3 (en) * | 1991-05-06 | 1993-11-10 | Hoechst Ag | Aqueous solutions of cationic polyamidoamine resins |
WO1992022601A1 (fr) * | 1991-06-19 | 1992-12-23 | Akzo N.V. | Resines a base d'epihalohydrine a teneur reduite en halogene |
EP0776923A2 (fr) * | 1991-06-19 | 1997-06-04 | Akzo Nobel N.V. | Résines à base d'épihalohydrines à teneur réduite en halogène |
EP0776923A3 (fr) * | 1991-06-19 | 1997-08-06 | Akzo Nobel Nv | Résines à base d'épihalohydrines à teneur réduite en halogène |
WO1993003222A1 (fr) * | 1991-08-05 | 1993-02-18 | Henkel Corporation | Composition de resine de resistance a l'etat humide et procede de preparation |
EP0703265A1 (fr) | 1994-07-22 | 1996-03-27 | Hoechst Aktiengesellschaft | Hydrogels hydrophiles à capacité de gonflement élevée |
US5972691A (en) * | 1995-06-07 | 1999-10-26 | Hercules Incorporated | Dehalogenation of polyamine, neutral curing wet strength resins |
US6107432A (en) * | 1997-05-28 | 2000-08-22 | Basf Ag | Water-swellable, hydrophilic polymer compositions |
WO1999009252A1 (fr) * | 1997-08-13 | 1999-02-25 | Fort James Corporation | Formulations de resines thermodurcissables resistant au mouille et polymeres de polyaminamide appropries pour l'emploi dans la fabrication de produits en papier |
US6222006B1 (en) | 1997-08-13 | 2001-04-24 | Fort James Corporation | Wet strength thermosetting resin formulations and polyaminamide polymers suitable for use in the manufacture of paper products |
US6429267B1 (en) | 1997-12-31 | 2002-08-06 | Hercules Incorporated | Process to reduce the AOX level of wet strength resins by treatment with base |
US6472478B1 (en) | 1998-02-21 | 2002-10-29 | Basf Aktiengesellschaft | Process for crosslinking hydrogels with bis- and poly-2- oxazolidinones |
US6503979B1 (en) | 1998-02-26 | 2003-01-07 | Basf Aktiengesellschaft | Method for cross-linking hydrogels with bis- and poly-2-oxazolidinones |
US6559239B1 (en) | 1998-11-26 | 2003-05-06 | Basf Aktiengesellschaft | Method for the secondary cross-linking of hydrogels with N-acyl-2-oxazolidinones |
US6657015B1 (en) | 1998-11-26 | 2003-12-02 | Basf Aktiengesellschaft | Method for the secondary cross-linking of hydrogels with 2-oxotetrahydro-1,3-oxazines |
US7175740B2 (en) | 1999-06-11 | 2007-02-13 | Hercules Incorporated | Reduced by product polyamine-epihalohydrin resins |
US7303652B2 (en) | 2000-12-09 | 2007-12-04 | Hercules Incorporated | Reduced byproduct high solids polyamine-epihalohydrin compositions |
US7183360B2 (en) | 2001-10-05 | 2007-02-27 | Basf Aktiengesellschaft | Method for crosslinking hydrogels with morpholine-2,3-diones |
US7655733B2 (en) | 2004-08-04 | 2010-02-02 | Basf Aktiengesellschaft | Postcrosslinking of water absorbing polymers with cyclic carbamates and/or cyclic ureas |
US7947771B2 (en) | 2004-11-30 | 2011-05-24 | Basf Aktiengesellschaft | Insoluble metal sulfates in water absorbing polymeric particles |
WO2008036241A1 (fr) | 2006-09-18 | 2008-03-27 | Hercules Incorporated | Procédé de séparation par membrane pour retirer des résidus provenant de résines polyamine-épihalohydrine |
Also Published As
Publication number | Publication date |
---|---|
EP0349935A3 (fr) | 1991-05-08 |
ES2058408T3 (es) | 1994-11-01 |
DE3822490A1 (de) | 1990-01-04 |
ATE90405T1 (de) | 1993-06-15 |
US5019606A (en) | 1991-05-28 |
DE58904602D1 (de) | 1993-07-15 |
EP0349935B1 (fr) | 1993-06-09 |
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