EP0948488A1 - Melanges de 4,5-dihydroxy-imidazolidin-2-ones methylolees alkylees - Google Patents
Melanges de 4,5-dihydroxy-imidazolidin-2-ones methylolees alkyleesInfo
- Publication number
- EP0948488A1 EP0948488A1 EP97954477A EP97954477A EP0948488A1 EP 0948488 A1 EP0948488 A1 EP 0948488A1 EP 97954477 A EP97954477 A EP 97954477A EP 97954477 A EP97954477 A EP 97954477A EP 0948488 A1 EP0948488 A1 EP 0948488A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- mixtures
- alcohol
- polyol
- dmdheu
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D233/28—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D233/30—Oxygen or sulfur atoms
- C07D233/32—One oxygen atom
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/402—Amides imides, sulfamic acids
- D06M13/432—Urea, thiourea or derivatives thereof, e.g. biurets; Urea-inclusion compounds; Dicyanamides; Carbodiimides; Guanidines, e.g. dicyandiamides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D233/28—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D233/30—Oxygen or sulfur atoms
- C07D233/40—Two or more oxygen atoms
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
Definitions
- the invention relates to mixtures of mixed-alkylated methylolated 4,5-dihydroxy-imidazolidin-2-ones.
- the invention also relates to a process for the preparation of said mixtures, finishing baths therefrom and their use.
- Methylolated 4,5-dihydroxy-imidazolidin-2-ones are used in textile finishing as low-formaldehyde crosslinkers. They are also described as DMDHEU compounds [see Ullmann's Encyclopedia of Industrial Chemistry, Vol. A 26, pages 227 to 350]. These textile crosslinkers bring about a good crease recovery and reduce the textile shrinkage. DMDHEU derivatives reacted with methanol provide good easy-care effects. At the same time, the formaldehyde content of the textiles treated with such DMDHEU derivatives is low. However, the disadvantage of this is high emissions from the user, i.e. in textile finishing, through a residual methanol content or through partially split off methanol.
- mixtures of mixed-alkylated methylolated 4,5-dihydroxy-imidazolidin-2-ones which can be prepared by reacting methylolated 4,5-dihydroxy-imidazolidin-2-ones (DMDHEU) with a monovalent C ⁇ Alcohol and a polyol selected from the group comprising ethylene glycol, diethylene glycol, 1,2- and 1,3-propylene glycol, 1,2-, 1,3- and 1,4-butylene glycol, glycerol and polyethylene glycols Formula HO (CH 2 CH 2 O) n H with 3 ⁇ n 20 20, the monohydric C 5 alcohol and the polyol being used in an amount of 0.1 to 2.0 molar equivalents, based on DMDHEU, and the Reaction takes place at temperatures of 20 ° C to 70 ° C and a pH of 1 to 2.5, and the pH is adjusted to a value of 4 to 8 after the reaction.
- DMDHEU methylolated 4,5-dihydroxy-imidazo
- the invention further provides a corresponding process for the preparation of these mixtures. Furthermore, an aqueous finishing bath for textile, cellulose-containing materials is provided according to the invention, comprising the mixtures according to the invention mentioned.
- DMDHEU is preferably unsymmetrically substituted on the two nitrogen atoms of the imidazoline ring.
- one of the two methylol groups of the DMDHEU is etherified with a methyl radical, while the other methylol group is selected from by reaction with a polyol of the group comprising ethylene glycol, diethylene glycol, 1,2- and 1,3-propylene glycol, 1,2-, 1,3- and 1,4-butylene glycol, glycerol and polyethylene glycols of the formula HO (CH 2 CH 2 O) n H is derivatized with 3 ⁇ n ⁇ 20, preferably diethylene glycol.
- the process according to the invention for the preparation of the mixtures comprises both a one-step and a two-step process.
- an aqueous solution of DMDHEU is first reacted with a monohydric C 1 -C 5 alcohol, preferably methanol.
- the reaction takes place with 0.1 to 2.0 molar equivalents of the alcohol.
- the pH during the reaction is in the range from 1 to 2.5.
- the temperature is 20 ° C to 70 ° C.
- the DMDHEU solution used has a solids content of usually 40 to 85% by weight.
- the reaction takes place in the presence of mineral acids, their mixtures or organic acids. Preferred acids are phosphoric acid or mixtures thereof with other mineral acids.
- the reaction times for the implementation are between 0.5 and 6 hours.
- the aqueous solution is in a second step also with 0.1 to 2.0 molar equivalents of a polyol, selected from the group consisting of ethylene glycol, diethylene glycol, 1,2- and 1,3-propylene glycol, 1,2-, 1st , 3- and 1,4-butylene glycol, glycerol and polyethylene glycols of the formula HO (CH 2 CH 2 O) n H with 3 ⁇ n ⁇ 20.
- the monohydric C 1-4 alcohol is preferably used in an amount of 0.7 to 2.0 molar equivalents and the polyol in an amount of 0.8 to 1.4 molar equivalents, in each case based on DMDHEU.
- the monohydric C 1 -C alcohol and the polyol are preferably used in a total amount of 1.7 to 2.9 molar equivalents, based on DMDHEU.
- the pH value and the temperature of the reaction in the second step lie within the ranges already mentioned in the first step.
- Diethylene glycol is used as the preferred polyol.
- the first method step and the second method step are advantageously reversed in their order.
- the pH is adjusted to 4 to 8 using a customary base, for example sodium hydroxide or potassium hydroxide.
- the solutions thus obtained are adjusted to a desired solids content between 40 and 85% by weight.
- the mixtures according to the invention can also be prepared in a one-step process by reacting aqueous solutions of DMDHEU with alcohol mixtures.
- Alcohol mixtures are understood to mean mixtures of the alcohol components mentioned above, namely the monohydric C 1 -C 5 alcohols and the polyols mentioned.
- the mixtures mentioned contain the monohydric C 1 -C 5 alcohols and the polyols used according to the invention in proportions of 0.1-2.0: 2.0-0.1 molar equivalents.
- the reaction takes place at a pH of 1 to 2.5 and temperatures of 20 to 70 ° C, preferably 20 to 50 ° C in the presence of mineral acids, their mixtures or organic acids.
- the one-stage reaction is preferably carried out in the presence of phosphoric acid or mixtures thereof with other mineral acids.
- the pH is adjusted to 4 to 8 after the reaction has ended using a customary base, for example sodium hydroxide or potassium hydroxide.
- a customary base for example sodium hydroxide or potassium hydroxide.
- CC 5 alcohol is also preferred in the one-step process methanol.
- the preferred polyol is again diethylene glycol.
- the mixtures according to the invention are used to finish textile, cellulose-containing materials.
- an finishing bath which contains the mixtures according to the invention together with other conventional constituents, such as catalysts such as magnesium chloride.
- a 4% solution (based on 100% solids) was prepared from the products, which still contains 1.2% magnesium chloride as a catalyst. contained.
- the test fabric (cotton) was impregnated with these solutions in a padder and the liquor absorption was limited to 75%. The mixture was then dried at 6-8% residual moisture at 120 ° C. The condensation took place in 4 min at 150 ° C.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Polyethers (AREA)
Abstract
L'invention concerne un procédé de préparation de mélanges de 4,5-dihydroxy-imidazolidin-2-ones méthylolées alkylées mélangées par réaction de 4,5-dihydroxy-imidazolidin-2-one (DMDHEU) méthylolée avec un alcool en C1-5 monovalent et un polyol sélectionné dans le groupe constitué d'éthylèneglycol, de diéthylèneglycol, de 1,2- et 1,2-propylèneglycol, de 1,2-, 1,3- et 1,4-butylèneglycol, de glycérine et des polyéthylèneglycols qui répondent à la formule HO(CH2CH2O)nH, dans laquelle 3≤n≤20. La quantité de alcool en C1-5 monovalent et de polyol s'élève respectivement à 0, à 2,0 équivalents en moles, par rapport à la DMDHEU, et la réaction est conduite à des températures de 20 °C à 70 °C, à une valeur de pH de 1 à 2,5, la valeur de pH étant ajustée après la réaction sur une valeur comprise entre 4 et 8.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19654739A DE19654739A1 (de) | 1996-12-30 | 1996-12-30 | Gemischt-alkylierte bzw. -hydroxyalkoxyalkylierte methylolierte 4,5-Dihydroxy-imidazolidin-2-one |
| DE19654739 | 1996-12-30 | ||
| PCT/EP1997/007318 WO1998029393A1 (fr) | 1996-12-30 | 1997-12-30 | Melanges de 4,5-dihydroxy-imidazolidin-2-ones methylolees alkylees |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0948488A1 true EP0948488A1 (fr) | 1999-10-13 |
Family
ID=7816415
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP97954477A Ceased EP0948488A1 (fr) | 1996-12-30 | 1997-12-30 | Melanges de 4,5-dihydroxy-imidazolidin-2-ones methylolees alkylees |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US6265589B1 (fr) |
| EP (1) | EP0948488A1 (fr) |
| JP (1) | JP2001507355A (fr) |
| KR (1) | KR20000062381A (fr) |
| CA (1) | CA2276391A1 (fr) |
| DE (1) | DE19654739A1 (fr) |
| WO (1) | WO1998029393A1 (fr) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2355729A (en) | 1998-03-24 | 2001-05-02 | Nano Tex Llc | Modified textile and other materials and methods for their preparation |
| DE19860204A1 (de) * | 1998-12-24 | 2000-06-29 | Basf Ag | Verfahren zur Herstellung von cellulosehaltigen textilen Materialien |
| DE10246400A1 (de) * | 2002-10-04 | 2004-08-05 | Georg-August-Universität Göttingen | Verfahren zur Verbesserung der Oberflächenhärte eines Holzkörpers mit einer wässrigen Lösung eines Imprägniermittels |
| DE10246401A1 (de) * | 2002-10-04 | 2004-08-05 | Georg-August-Universität Göttingen | Verfahren zur Verbesserung der Dauerhaftigkeit, Dimensionsstabilität und Oberflächenhärte eines Holzkörpers |
| DE10335673B4 (de) | 2003-08-04 | 2007-01-18 | Celanese Emulsions Gmbh | Wässrige Dispersionsklebstoffe, Verfahren zu deren Herstellung und deren Verwendung |
| DE102004031530A1 (de) * | 2004-06-29 | 2006-02-09 | Basf Ag | Verfahren zum Kolorieren von textilen Substraten, wässrige Vorbehandlungsflotten und ihre Verwendung zur Vorbehandlung von textilen Substraten |
| DE102005050658A1 (de) * | 2005-10-20 | 2007-04-26 | Basf Ag | Verfahren zur Verminderung der Absorption von Wasser und Wasserdampf und zur Erhöhung der Dimensionsstabilität von Papier und Papierprodukten und Verwendung von beschichteten Papierprodukten |
| EP2239322A1 (fr) | 2009-04-07 | 2010-10-13 | Basf Se | Utilisation d'enzymes pour réduire le formaldéhyde dans des produits contenant du formaldéhyde |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3091617A (en) * | 1961-02-03 | 1963-05-28 | American Cyanamid Co | Process for preparing 4, 5-dialkoxy-1, 3-dialkyl-2-imidazolidinones |
| BE614590A (fr) * | 1961-02-03 | 1900-01-01 | ||
| CH507950A (de) * | 1968-03-14 | 1971-05-31 | Sumitomo Chemical Co | Verfahren zur Herstellung eines Kondensationsproduktes |
| US4295846A (en) * | 1980-03-18 | 1981-10-20 | Basf Aktiengesellschaft | Process for the production of formaldehyde-free finishing agents for cellulosic textiles and the use of such agents |
| US4396391B2 (en) * | 1982-06-30 | 1993-03-16 | Treating cellulose textile fabrics with dimenthylol dihydroyethyleneuree-polyol | |
| NL8701308A (nl) * | 1987-06-04 | 1989-01-02 | Dsm Resins Bv | Ureumderivaat en een harssamenstelling op basis van dit ureumderivaat. |
| US5160503A (en) * | 1989-11-13 | 1992-11-03 | West Point Pepperell | Water-soluble blends of active methylene compounds and polyhydric alcohols as formaldehyde scavengers |
| US5352372A (en) * | 1993-02-02 | 1994-10-04 | Sequa Chemicals, Inc. | Textile resins with reduced free formaldehyde |
-
1996
- 1996-12-30 DE DE19654739A patent/DE19654739A1/de not_active Withdrawn
-
1997
- 1997-12-30 JP JP52962198A patent/JP2001507355A/ja active Pending
- 1997-12-30 US US09/331,583 patent/US6265589B1/en not_active Expired - Fee Related
- 1997-12-30 WO PCT/EP1997/007318 patent/WO1998029393A1/fr not_active Ceased
- 1997-12-30 CA CA002276391A patent/CA2276391A1/fr not_active Abandoned
- 1997-12-30 KR KR1019997005937A patent/KR20000062381A/ko not_active Ceased
- 1997-12-30 EP EP97954477A patent/EP0948488A1/fr not_active Ceased
Non-Patent Citations (1)
| Title |
|---|
| See references of WO9829393A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2001507355A (ja) | 2001-06-05 |
| US6265589B1 (en) | 2001-07-24 |
| CA2276391A1 (fr) | 1998-07-09 |
| WO1998029393A1 (fr) | 1998-07-09 |
| KR20000062381A (ko) | 2000-10-25 |
| DE19654739A1 (de) | 1998-07-02 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| 17P | Request for examination filed |
Effective date: 19990715 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH DE ES FR GB IT LI NL |
|
| 17Q | First examination report despatched |
Effective date: 20020319 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION HAS BEEN REFUSED |
|
| 18R | Application refused |
Effective date: 20060527 |