EP0746630B1 - Verwendung sulfierter substanzen zur fettung von leder - Google Patents
Verwendung sulfierter substanzen zur fettung von leder Download PDFInfo
- Publication number
- EP0746630B1 EP0746630B1 EP95908273A EP95908273A EP0746630B1 EP 0746630 B1 EP0746630 B1 EP 0746630B1 EP 95908273 A EP95908273 A EP 95908273A EP 95908273 A EP95908273 A EP 95908273A EP 0746630 B1 EP0746630 B1 EP 0746630B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- sulfuric acid
- acids
- substances
- sulfonic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Classifications
-
- 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
- C14C9/02—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes using fatty or oily materials, e.g. fat liquoring
Definitions
- the invention relates to the use of special sulfated substances leather greasing. These substances are reaction products of mono- or polybasic carboxylic acids with 12 to 72 carbon atoms or mixtures of such carboxylic acids with a sulfonating reagent from at least an organic sulfonic acid and sulfuric acid.
- fatty acids are the main aids to to shape the character of leather.
- the effect of the fatliquor comes due to fiber-insulating lubrication and hydrophobization.
- the mutual Friction decreases and, consequently, suppleness and elasticity of the tissue improved. This has positive effects on the tensile strength of leather, because straighten in a stretchy material many fibers in tensile stress in the tensile direction and then settle more resistance to tearing than the same fibers within of a brittle material.
- Vegetable and animal leather greases are generally used Oils, fats and waxes are used, as well as those made from these substances by chemical Conversion obtained hydrolysis, sulfation, oxidation and Hardening products and finally mineral greasing agents; in detail:
- the saponifiable fats and oils as well as the natural waxes and resins belong to the esters.
- oils and fats are the leather specialist Glycerin and fatty acid esters are termed solid at room temperature or are liquid.
- the leather greasing from the group of animal Fats in particular, tears, fish oil, beef tallow and beef claw oil, from the group of vegetable fats castor oil, rape oil and linseed oil.
- the fatty acids are included instead of with glycerin higher molecular alcohols esterified.
- waxes are beeswax, Chinese wax, carnauba wax, montan wax and wool fat; to the main resins include rosin, yeast oil and shellac.
- Mineral greasing agents are also important for leather production. These hydrocarbons are in the natural fats and oils Similar to some properties, but cannot be saponified. It deals fractions of petroleum distillation, the liquid mineral oil, called petroleum jelly in pasty form and paraffin in solid form will.
- licker oils are self-emulsifying Products containing a neutral oil and an emulsifier in an aqueous medium contain.
- the emulsifier can either separate the licker oil Be admixed component or by partial sulfonation of the neutral oil have been produced.
- Examples of means for greasing leather after this classic and still important processes are manufactured sulfated claw oil, sulfated lard oil and rapeseed oil, sulfated fish oil and sulfated beef tallow.
- sulfation Amounts of concentrated sulfuric acid used are typically in the range from 15 to 60% by weight, based on the oil to be sulfated (cf. Hans Herfeld, ed., "Bibliothek des Leders, Frankfurt 1987, volume 4, pages 77-78).
- the classic sulfation process however, has the disadvantage that it is complex and requires time-consuming refurbishment measures.
- the reason is in that the fats and oils to be sulfated are included in practice on these fats and oils - the aforementioned high amounts of concentrated Sulfuric acid, for fish oil e.g. with approx. 20% by weight in contact to be brought. Only part of the sulfuric acid reacts, the rest - usually the majority - is unchanged after the reaction Form before. After neutralization with NaOH usually lies accordingly then a large amount of sodium sulfate. The consequence of which is that the products are not stable in storage. Under lack of storage stability it is understood that a separation into several phases occurs. The aqueous phase contains a large part of the respective inorganic Salts, e.g. As sodium sulfate or ammonium sulfate.
- the post-processing serves the purpose of adding a large part of the salt remove. This is usually done by neutralizing it First wash the sulfation product with water. Then disconnects the (salt-rich) aqueous phase from the (salt-poor) oil phase. The process however, phase separation is difficult to do in practice and time consuming. In addition, the resulting wash water polluting both with regard to the salt load contained therein, and also with regard to the (small) amounts of sulfated Products. This corresponds to that in the course of classic sulfation processes required postprocessing neither in economic nor in ecological Regarding the requirements of modern and efficient today and at the same time as environmentally friendly production methods as possible be put.
- DE-A-41 41 532 describes a process for producing hydrophylized Triglycerides known to be saturated, unsaturated and / or blown Triglycerides initially in the presence of glycerin and alkaline catalysts reacted with ethylene oxide, the resulting ethoxylated triglycerides sulfated with gaseous sulfur trioxide and the resulting acidic sulfonation products then neutralized with aqueous bases. After According to the teaching of DE-A-41 41 532, the products thus produced are suitable for Leather greasing.
- a very important need in practice is greasy substances or to provide equipment that is in the tanned Skin substance can be bound so reliably that one for the practical needs sufficient resistance to washing and cleaning the leather and fur goods are guaranteed.
- High quality leather goods for example from the clothing industry, both aqueous-surfactant laundry and, if necessary, chemical cleaning be accessible without significant loss of quality.
- Fogging means that in Over time, volatile substances escape from the leather and settle in precipitate undesirably, e.g. on windshields.
- Fogging-real substances is understood to mean that these substances, on the one hand are so tightly bound inside the leather that they are practically not are volatile, on the other hand, that these substances have the fogging characteristic improve usual fatliquor or fatlip constituents, i.e. reduce their fogging values.
- EP-A-498 teaches 634 a treatment of the leather with aqueous dispersions that are free of organic solvents and which contain an amphiphilic copolymer, that of at least one hydrophilic monomer and at least one hydrophobic monomer.
- the object of the present invention was to provide substances which are suitable for greasing leather.
- greasing equipment is on the one hand the leather greasing in the narrow To understand literal sense, as well as the hydrophobization of leather.
- Another task was to treat these substances with the that is, licked leather has good properties Giving scar firmness, fullness, lardiness and that subsequently colored leather is characterized by an unlightened, level shade.
- Another task was to ensure that these substances good storage stability.
- the present invention accordingly relates to the use sulfated substances for greasing leather, the sulfated Substances are available through the implementation of mono- or polybasic Carboxylic acids a) with 12 to 72 carbon atoms, with a sulfonating agent b) in addition to subsequent neutralization.
- the sulfonating reagent b) is used a combination of at least one organic sulfonic acid bl) and sulfuric acid b2), with the proviso that the proportion of sulfuric acid - Based on the sum of organic sulfonic acid and sulfuric acid - 0.5 to 80 wt .-%.
- the invention is subject to no restrictions at all. As particularly important embodiments may be mentioned the fatty acids, the dicarboxylic acids and the dimer or trimer fatty acids.
- Fatty acids are - as is generally the case in the specialist world (see, for example, 0.-A.Neumüller, Römpps Chemie-Lexikon, Stuttgart 1973, p.1107ff) - all aliphatic, monobasic carboxylic acids, which are both saturated and unsaturated can.
- fatty acids which are suitable as fatty acid building blocks of esters a) are formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, oenanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, palmitic acid stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, cerotic, melissic, isobutyric, isovaleric acid, acrylic acid, methacrylic acid, crotonic acid, 10-undecenoic, lauroleic acid, myristoleic acid, palmitoleic acid, oleic acid, petroselinic acid, elaidic acid, ricinoleic acid, sorbic acid, linoleic acid, Linolaidin
- Dicarboxylic acids are understood to mean dibasic organic carboxylic acids. Preferred are those with 2 to 24 carbon atoms and in particular those which - in the sense of the classic definition of "Römpp" (see, for example, 0.-A.Neumüller, Römpps Chemie-Lexikon, Stuttgart 1973, p.828f ) - Derive from linear paraffins in that both ends are oxidized to carboxyl groups.
- dicarboxylic acids examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, furthermore maleic acid, fumaric acid, phthalic acid and terephthalic acid.
- dicarboxylic acids containing OH groups for example malic acid, are preferred.
- Dimer fatty acids - as is customary in the art - are understood to mean those carboxylic acids which are accessible by oligomerizing unsaturated carboxylic acids, generally fatty acids such as oleic acid, linoleic acid, erucic acid and the like.
- the oligomerization is usually carried out at elevated temperature in the presence of a catalyst made of, for example, alumina.
- the products obtained are mixtures of different substances, with the dimersization products predominating.
- small amounts of higher oligomers, in particular the trimer fatty acids are also present.
- Dimer fatty acids are commercially available products and are offered in various compositions and qualities. In the context of the present invention, those dimer fatty acids are preferred which have a dimer content of at least 50%, preferably 75% and in which the number of carbon atoms per dimer molecule is predominantly in the range from 36 to 44.
- trimer fatty acids are also commercially available products.
- Preferred trimer fatty acids are those in which the trimer content is at least 50%, preferably 75%.
- component a) is at least partially ethylenically unsaturated.
- “At least partially ethylenically unsaturated” is understood to mean that the iodine number of the carboxylic acid a) is at least 5.
- the iodine number of the carboxylic acid a) is limited in practice by values in the range from approximately 300 to 400.
- those carboxylic acids or carboxylic acid mixtures a) are generally used whose iodine number is in the range from 40 to 260.
- the quantitative ratios can of carboxylic acid a) and sulfonating reagent b) within wide limits vary.
- the quantitative ratios these components are set to range from 1:99 to 99: 1.
- a range is a): b) from 10: 1 to 1:10 and in particular a range from 4: 1 to 1: 4 is preferred.
- the sulfonated substances according to the invention are very general due to good greasy or hydrophobic properties as well with good fogging characteristics.
- the carboxylic acids a) can be used in the form of commercially available products will.
- leather is also sufficient in qualities such as those found in Distillation residues of the fatty acid production are present.
- the component to be sulfated is used a) in the form of a mixture of at least one carboxylic acid a) and at least a lower alkyl ester of a fatty acid liquid at 20 ° C with 8 up to 24 carbon atoms.
- a lower alkyl ester is understood to mean that the alcohol component of the ester has at most 8 carbon atoms, the range from 1 to 4 carbon atoms is preferred.
- the fatty acid lower alkyl ester can be in saturated or with respect to its alcohol and / or fatty acid building blocks (ethylenically) unsaturated.
- This embodiment has the advantage that the task of the fatty acid lower alkyl ester is carboxylic acids a) which are completely or partially solid at 20 ° C, liquefy or at least in to bring a homogeneous and flowable state, so that the Allow mixture to stir gently, possibly after slightly warming up.
- a further embodiment of the present invention consists in reacting those carboxylic acids a) with the sulfonating reagent b) which are alkoxylated and / or epoxidized.
- carboxylic acids a) with the sulfonating reagent b) which are alkoxylated and / or epoxidized.
- ethylene oxide, propylene oxide and butylene oxide or mixtures thereof can be used as building blocks for the alkoxylation.
- the ethoxylated fatty acids which are derived formally from the addition of one or more -CH 2 -CH 2 -O groups.
- These compounds can be prepared in various ways, for example by reacting the fatty acids with ethylene oxide in the presence of a catalyst (classic ethoxylation) or by reacting the fatty acids with polyethylene oxide in the presence of a catalyst.
- a combination of at least one organic sulfonic acid b1) and sulfuric acid b2) is used as the sulfonating reagent b) ; the proportion of sulfuric acid - based on the sum of organic sulfonic acid and sulfuric acid - is 0.5 to 80% by weight. However, a sulfuric acid content of 1 to 40 and in particular 5 to 20% by weight is preferred.
- sulfuric acid there are no restrictions on the nature of sulfuric acid. So can be dilute sulfuric acid, concentrated sulfuric acid or fuming Sulfuric acid (concentrated sulfuric acid, the varying amounts of Contains dissolved sulfur trioxide, the so-called oleum). It is preferred to use sulfuric acid at a concentration in the range of 96 up to 98% by weight or oleum.
- organic sulfonic acids b1) is in itself not subject to any particular one Restrictions.
- suitable sulfonic acids are alkane or Haloalkanesulfonic acids such as methanesulfonic acid, ethanesulfonic acid, Propanesulfonic acid, butanesulfonic acid, long-chain alkanesulfonic acids, chlorosulfonic acid, also naphthalenesulfonic acid, alpha-sulfo fatty acids (available e.g. by reacting saturated fatty acids with gaseous sulfur trioxide), alpha-sulfo fatty acid alkyl esters, e.g. -methyl ester (available e.g. by reacting saturated fatty acid alkyl esters with gaseous Sulfur trioxide).
- aromatic sulfonic acids are used as Component b2).
- Alkylbenzenesulfonic acids and in particular the commercially available linear alkyl benzyl sulfonic acid are particularly preferred.
- the carboxylic acids a) are finally reacted with a sulfonating reagent b) which consists of a ternary combination of at least one organic sulfonic acid b1), sulfuric acid b2) and at least one hydrogen sulfate b3) (older name: bisulfate).
- a sulfonating reagent b) which consists of a ternary combination of at least one organic sulfonic acid b1), sulfuric acid b2) and at least one hydrogen sulfate b3) (older name: bisulfate).
- Suitable hydrogen sulfates are compounds of the structure Alk-HSO 4 , where "Alk" means a monovalent metal or NH 4 .
- Preferred monovalent metals are the alkali metals, especially sodium and / or potassium.
- Another object of the present invention is a method for Production of sulfated substances, using mono- or polybasic carboxylic acids a) with 12 to 72 carbon atoms, with a sulfonating reagent b) and the reaction mixture is then neutralized, the reaction being carried out at temperatures in the range of 20 to 130 ° C and as Sulfierreagens b) a combination of at least one organic sulfonic acid b1) and sulfuric acid b2) is used, with the proviso that the proportion sulfuric acid - based on the sum of organic sulfonic acid and Sulfuric acid - 0.5 to 80 wt .-%.
- the process according to the invention has the advantage that it is usually only moderate reaction temperatures required.
- the reaction temperature is only in the range from 20 to 80 ° C and especially 20 to 40 ° C.
- the reaction continues combining components a) and b) spontaneously with the release of Heat, so that in these cases cooling must even be carried out in order to achieve a controlled Ensure the course of the reaction.
- reaction times are relative in short, usually on the order of 1 to 4 hours. It can but - depending on the nature of the component a) used - reaction times below one hour or above may also be desirable of 4 hours.
- the process is usually carried out in such a way that the Components a) and b) mixed together at about 20 ° C. Often sets an exothermic reaction - particularly strong in those cases where the sulfating reagent from a mixture of aromatic sulfonic acids and There is sulfuric acid.
- the reaction mixture is now stirred at a slightly elevated temperature.
- the method according to the invention is used at lowest possible temperature. This is in cases where 20 ° C liquid carboxylic acids are used as component a) and where the Proportion of sulfuric acid in the sulfonating reagent b) in the preferred range of 1 to 40 wt .-%, preferably in the range of 20 to 40 ° C, wherein often has to cool externally to keep the temperature in this range.
- carboxylic acids a which are not at 20 ° C or slightly elevated temperature are sufficiently liquid, or where the reaction is to conclude as quickly as possible may be brought, however, the entire mentioned temperature range from 20 to 80 ° C or 20 to 130 ° C to take advantage of.
- the reaction may even be desirable perform at higher temperatures (up to approx. 250 ° C), e.g. B. if one as component a) uses carboxylic acids with a high melting point, but on wants to dispense with the possible addition of a diluent or if the reaction rate should be increased even further. In the area at these high reaction temperatures, it may be appropriate the reaction in the presence of air in an inert gas atmosphere (e.g. under Nitrogen).
- an inert gas atmosphere e.g. under Nitrogen
- neutralization closes on.
- the reaction mixture is allowed to cool and then doses the desired base.
- suitable bases are Alkali metal hydroxides, alkaline earth metal hydroxides, ammonium hydroxide, alkanolamines and alkylamines or mixtures thereof. Are preferred especially sodium hydroxide, potassium hydroxide and ammonium hydroxide. A further processing of the neutralized products is not necessary.
- carboxylic acid e.g. F-1 to F-8
- sulfonating agent e.g. S-1 to S-3
- carboxylic acid e.g. F-1 to F-8
- S-1 to S-3 sulfonating agent
- the carboxylic acid used is liquid at room temperature, is stirred for about 2 hours, a temperature in the range of 20 up to 40 ° C. In the case of exothermic reactions, the corresponding chilled.
- carboxylic acids that are solid, partially solid at 20 ° C or are viscous e.g. carboxylic acid F-6
- you choose a reaction temperature in which the carboxylic acid is liquid.
- a Temperature set at a maximum of 80 ° C.
- the reaction mixture neutralized with a base (e.g. 37% by weight aqueous sodium hydroxide solution), if necessary after cooling the mixture beforehand.
- a base e.g. 37% by weight aqueous sodium hydroxide solution
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Coloring (AREA)
- Lubricants (AREA)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4405416A DE4405416A1 (de) | 1994-02-21 | 1994-02-21 | Verwendung sulfierter Substanzen zur Fettung von Leder |
DE4405416 | 1994-02-21 | ||
PCT/EP1995/000511 WO1995022632A1 (de) | 1994-02-21 | 1995-02-13 | Verwendung sulfierter substanzen zur fettung von leder |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0746630A1 EP0746630A1 (de) | 1996-12-11 |
EP0746630B1 true EP0746630B1 (de) | 1998-09-23 |
Family
ID=6510719
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP95908273A Expired - Lifetime EP0746630B1 (de) | 1994-02-21 | 1995-02-13 | Verwendung sulfierter substanzen zur fettung von leder |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0746630B1 (tr) |
AT (1) | ATE171481T1 (tr) |
DE (2) | DE4405416A1 (tr) |
TR (1) | TR28870A (tr) |
WO (1) | WO1995022632A1 (tr) |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1768548A1 (de) * | 1968-05-25 | 1971-11-18 | Henkel & Cie Gmbh | Verfahren zur Herstellung von Sulfonierungsprodukten |
DE3617657C2 (de) * | 1986-05-26 | 1994-08-18 | Stockhausen Chem Fab Gmbh | Bei Raumtemperatur flüssige Derivate von natürlichen Fetten oder Ölen, Verfahren zu deren Herstellung, und ihre Verwendung |
HRP930646A2 (en) * | 1992-04-10 | 1994-10-31 | Hoechst Ag | Leather greasing material |
-
1994
- 1994-02-21 DE DE4405416A patent/DE4405416A1/de not_active Withdrawn
-
1995
- 1995-02-13 AT AT95908273T patent/ATE171481T1/de active
- 1995-02-13 EP EP95908273A patent/EP0746630B1/de not_active Expired - Lifetime
- 1995-02-13 WO PCT/EP1995/000511 patent/WO1995022632A1/de active IP Right Grant
- 1995-02-13 DE DE59503704T patent/DE59503704D1/de not_active Expired - Fee Related
- 1995-02-16 TR TR00156/95A patent/TR28870A/tr unknown
Also Published As
Publication number | Publication date |
---|---|
TR28870A (tr) | 1997-07-17 |
EP0746630A1 (de) | 1996-12-11 |
WO1995022632A1 (de) | 1995-08-24 |
DE4405416A1 (de) | 1995-10-05 |
DE59503704D1 (de) | 1998-10-29 |
ATE171481T1 (de) | 1998-10-15 |
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