CA2021758A1 - Use of copolymers based on long-chain olefins and ethylenically unsaturated dicarboxylic anhydrides for rendering leathers and skins water-repellent - Google Patents
Use of copolymers based on long-chain olefins and ethylenically unsaturated dicarboxylic anhydrides for rendering leathers and skins water-repellentInfo
- Publication number
- CA2021758A1 CA2021758A1 CA002021758A CA2021758A CA2021758A1 CA 2021758 A1 CA2021758 A1 CA 2021758A1 CA 002021758 A CA002021758 A CA 002021758A CA 2021758 A CA2021758 A CA 2021758A CA 2021758 A1 CA2021758 A1 CA 2021758A1
- Authority
- CA
- Canada
- Prior art keywords
- copolymer
- carboxyl groups
- water
- total amount
- groups formed
- 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.)
- Abandoned
Links
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
Abstract
O.Z. 0050/41004 Abstract of the Disclosure: Copolymers which are obtain-able by free radical copolymerization of (a) C8-C40-monoolefins with (b) ethylenically unsaturated C4-C8-dicarboxylic anhydrides by mass polymerization at from 80 to 300°C to give copolymers having molecular weights of from 500 to 20,000 g/mol, subsequent solvolysis of the anhydride groups of the copolymers and partial or com-plete neutralization of the carboxyl groups formed during the solvolysis, in an aqueous medium by means of a base, and which are present in the form of aqueous dispersions or solutions, are used as agents for rendering leathers and skins water-repellent.
Description
O.Z. 0050/41004 Use of copol,~ers based on lonq-chain olefin~
and ethvlenically unsaturated dicarboxylic anhydrides for renderina leathers and skin~
water-repellent S German Laid-Open Application DOS 3,730,885 dis-closes fuels for ga~oline engines which contain, inter alia, small amountq of copolymers of olefins of 2 to 40 carbon atomq and maleic anhydride and have a molecular weight of from 500 to 20,000 g/mol and in which some or all of the anhydride groups of the copolymers have been reacted with aqueous alkali me~al or alkaline earth metal baseq and the remainder of the carboxyl group~ have been converted with alcohols and/or amine~ into the corres-ponding ester and/or amide groups andtor ammonium salts.
German Patent 2,629,748 disclose~ the use of co-polymers of C1O-C~0-olefins and maleic anhydride, which are : hydrolyzed with alkali matal ba~es or amines, for filling and fatliquoring leathers and ~kins. The hydrolyzed copolymers can also b~ reacted with alkali metal bisul-fites. Since the copolymers are prepared in organic sol-vents and the solvents are not removed, the aqueous copolymer dispersions prepared therefrom contain con-siderable amounts of organic olvents, for example xylene or dodecylbenzene. Although such disper~ion~ are suit-able for fatliquoring leather~ and ~kins, owing to their content of organic solvents they are virtually useless for rendering leather~ and s~ins water-repell2nt.
It iq an ob~ect of the pre~ent i~vention to pro-vide an improved aqent for rendering leathers and skin~
water-repellent.
; W~ have found thaf this object is achieved, according to the invention, by the use of copolymers which are obtainable by free radical copolymerization of (a) C9-C4~-monoolefins with (b) ethylenically unsaturated C4-C8-dicarboxylic anhyd rides, : by a mass pol~merization method at from 80 to 300C, to .
and ethvlenically unsaturated dicarboxylic anhydrides for renderina leathers and skin~
water-repellent S German Laid-Open Application DOS 3,730,885 dis-closes fuels for ga~oline engines which contain, inter alia, small amountq of copolymers of olefins of 2 to 40 carbon atomq and maleic anhydride and have a molecular weight of from 500 to 20,000 g/mol and in which some or all of the anhydride groups of the copolymers have been reacted with aqueous alkali me~al or alkaline earth metal baseq and the remainder of the carboxyl group~ have been converted with alcohols and/or amine~ into the corres-ponding ester and/or amide groups andtor ammonium salts.
German Patent 2,629,748 disclose~ the use of co-polymers of C1O-C~0-olefins and maleic anhydride, which are : hydrolyzed with alkali matal ba~es or amines, for filling and fatliquoring leathers and ~kins. The hydrolyzed copolymers can also b~ reacted with alkali metal bisul-fites. Since the copolymers are prepared in organic sol-vents and the solvents are not removed, the aqueous copolymer dispersions prepared therefrom contain con-siderable amounts of organic olvents, for example xylene or dodecylbenzene. Although such disper~ion~ are suit-able for fatliquoring leather~ and ~kins, owing to their content of organic solvents they are virtually useless for rendering leather~ and s~ins water-repell2nt.
It iq an ob~ect of the pre~ent i~vention to pro-vide an improved aqent for rendering leathers and skin~
water-repellent.
; W~ have found thaf this object is achieved, according to the invention, by the use of copolymers which are obtainable by free radical copolymerization of (a) C9-C4~-monoolefins with (b) ethylenically unsaturated C4-C8-dicarboxylic anhyd rides, : by a mass pol~merization method at from 80 to 300C, to .
2 V ~ 8 - 2 - O.Z. 0050/41004 give a copolymer having a molecular weight of from 500 to 20,000 g/mol, subsequent solvolysis of the anhydride groups of the copolymer and partial or complete neutral-ization of the carboxyl groups formed during the solvo-lysis, in an aqueous medium by means of a base, and which is present in the form of a 0.5-50% strength by weight aqueou~ dispersion, as an agent for rendering leathers and skins water-repellent.
The copol~mers are disclosed in, for example, German Laid-Open Application DOS 3,730,885. They are prepared by a mass polymerization method by copolymeriza-tion of the monomers of group (a) with the monomers of group (b) at from 80 to 300C. Examples of suitable monoolefins of 8 to 40 carbon atoms are n-oct-l-ene, 2,4,4-trime~hylpent-1-ene, 2,4,4-trLmethylpent-2-ene, diisobutene, which is available industrially as an isomer mixture of about 80~ by weight of 2,4,4-trLmethylpent-1-ene and about 20% by weight of 2,4,4-trimethylpent-2-ene, 4,4-dime~hylhex-1-ene, dec-l-ene, dodec-l-ene, tetradec-1-ene, hexadec-l-ene, octadec-1-ene, l-(C20-olefins), 1-(C22-olefins), l-~C24-olef in8 ), 1- (C2~-C24-olefins), l-(C24-C2a-olefins), l-(C30-olefins), 1-(C35-olefins) and l-tC40-olefins~. The olefins or mixtures o olefins are commer-cial products. In addition to the straight-chain olefins, cyclic olefins, such a~ cyclooctene, ar~ also suitabls.
The olefin~ may contain ~mall smounts, for e~ample not more than about 5% by weight, of inert hydrocarbons from the preparation. The olefin~ are usually used in the commercially available quality. They need not be sub-~ected to any special puxification. The preferred olefins are Cl5-C30-olefins.
Suitable components (b) of the copolymers are monoethylenically unsaturat~d C4-Ca-dicarboxylic anhyd-rides, eg. maleic anhydride, itaconic anhydride, mesa-: 35 conic anhydride, citraconic anhydride and methylene-malonic anhydride and mixture~ thereof. Among the stated anhydrides, maleic anhydride i5 preferably used. The 2 ~
The copol~mers are disclosed in, for example, German Laid-Open Application DOS 3,730,885. They are prepared by a mass polymerization method by copolymeriza-tion of the monomers of group (a) with the monomers of group (b) at from 80 to 300C. Examples of suitable monoolefins of 8 to 40 carbon atoms are n-oct-l-ene, 2,4,4-trime~hylpent-1-ene, 2,4,4-trLmethylpent-2-ene, diisobutene, which is available industrially as an isomer mixture of about 80~ by weight of 2,4,4-trLmethylpent-1-ene and about 20% by weight of 2,4,4-trimethylpent-2-ene, 4,4-dime~hylhex-1-ene, dec-l-ene, dodec-l-ene, tetradec-1-ene, hexadec-l-ene, octadec-1-ene, l-(C20-olefins), 1-(C22-olefins), l-~C24-olef in8 ), 1- (C2~-C24-olefins), l-(C24-C2a-olefins), l-(C30-olefins), 1-(C35-olefins) and l-tC40-olefins~. The olefins or mixtures o olefins are commer-cial products. In addition to the straight-chain olefins, cyclic olefins, such a~ cyclooctene, ar~ also suitabls.
The olefin~ may contain ~mall smounts, for e~ample not more than about 5% by weight, of inert hydrocarbons from the preparation. The olefin~ are usually used in the commercially available quality. They need not be sub-~ected to any special puxification. The preferred olefins are Cl5-C30-olefins.
Suitable components (b) of the copolymers are monoethylenically unsaturat~d C4-Ca-dicarboxylic anhyd-rides, eg. maleic anhydride, itaconic anhydride, mesa-: 35 conic anhydride, citraconic anhydride and methylene-malonic anhydride and mixture~ thereof. Among the stated anhydrides, maleic anhydride i5 preferably used. The 2 ~
- 3 - O.Z. 0050/41004 copolymers contain from 40 to 60 mol % of monoolefins and from 60 to 40 mol % of the stated dicarboxylic anhydrides as polymeriæed units and have a molecular weight of from 500 to 20,000, preferably from 800 to 10,000, g/mol.
They are obtainable by polymerization of the monomers (a) and (b) in a molar ratio of from 1.1 : 1 to 1 : 1. The monomers (a) and (,b) are preferably polymerized in a molar ratio of 1 : 1 or only a 1~ by weight excess of monomers of component (a) is used. The monomers of groups (a) and (b) are known to foxm alternating copoly-mers which, in the case of high molecular weights, contain 50 mol % of monomers (a) and 50 mol % of monomers (b) as polymerized units. In the case of very low molecular weights of the copolymers, the molar ratio may differ from the abovementioned range, depending on the type of terminal groups, if, for example, the copolymer chain star~s with the monomers ~a) and also ends with the monomers (a).
Mass polymerization is carried out at from 80 to 300C, preferably from 120 to 200C, the lowest polymerization temperature chosen preferably being at least about 20C above the glass transition temperature of the polymer formed. The polymerization condition~ are chosen according to the desired molecular weight of the copolymers. Polymerization at high temperatures gives copolymers having low molecular weight~ whereas polymers having higher molecular weights ar~ formed at lower poly-merization temperatures. The amount of polymerization initiator also has an effect on the molecular weight. In general, from 0.01 to 5~ by weight, based on the monomers used in the polymerization, of free radical polymeriza-tion initiators are required. Larger ~mounts of initia-~or lead to copolymers having lower molecular weights.
At above 200C, the monomer~ la) and (b) can also be copolymerized in the absence of polymerization initia-tors, ie. it is not absolutely e~sential to use initia-tors, because the monnmer~ (a) and tb~ undergo free -2~2~
- ~ - O.Z. 0050/41004 radical polymerization also in the absence of initiators at above 200C. Examples of suitable polymerization initiators are di-tert-butyl peroxide, acetylcyclohexane-sulfonyl peroxide, diacetyl peroxydicarbonate, dicyclo-hexyl peroxydicarbonate, di-2-ethylhexyl peroxydi-carbonate, tert-butyl perneodecanoate, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile)~ tert-butyl perpiva-late, tert-butyl per-2-ethylhexanoate, tert-bukyl per-maleate, 2,2'-azobisisobutyronitrile, bis-(tert-butyl-peroxy)-cyclohexane,tert-butylperoxyisopropylcarbonate, tert-butyl peracetate, di-tert-butyl peroxide, di-tert-amyl peroxide, cumene hydroperoxide and tert-butyl hydroperoxide. The initiators can be used alone or as a mixture with one another. In mass polymerization, they are preferably introduced into the polymerization reactor separately or in the form of a solution or dispersion in the monoolefin. In ~he copolymerization, it is of course also possible to use redox coini~iators, for example benzoin, dimethylaniline, ascorbic acid and complexes of heavy metals, such as copper, cobalt, iron, manganese, nickel and chromium, which complexes are soluble in organic solvents. The presence of redox coinitiators permits the polymerization to be carried out at lower temperatures. The amounts of redox coinitiator~ usually ; 25 used are about 0.1-2000 ppm, preferably 0.1-1000 ppm, based on the amount~ o monomers ~lsed. If the monomer mixture ic initially polymerized at the lower limit of the temperature range suitable for the polymerization and then completely polymerized at a higher temperature, it is advantageou~ to u~e twc or more different initiators which decompose at different temperatures, so that a sufficient concentration o free radicals i5 a~ailabl.9 within each temperature range.
In order to prepare low molecular weight poly-mer~, it is often advantageou~ to carry out ~he copoly-merization in the presence of regulator Conventional regulators may be used for thi~ purpose, for example 2 0 ~
- 5 - O.Z. 0050/41004 Cl-C4-aldehydes, ormic acid a~d compound~ containing or-ganic SH groups, such as 2-mercaptoethanol, 2-mercapto-propanol, mercaptoacetic acid, mercaptopropionic acid, tert-butyl mercaptan, n-dodecyl mercaptan and tert-dodecyl mercaptan. Polymerizatlon regulators are gener-ally used in amounts of from 0.1 to 10% by weight, based on the monomers.
The copolymerization is carried out in conven-tionalpolymerization apparatuses, for example a pressure-resistant kettle which is provided with a stirrer, in pressure-resistant stirred kettle cascades or in a tubular reactor. In the case of mass polymerization, the olefins and the anhydrides are copolymerized in an equi-molar ratio in the absence of solvents. The copoly-merization can be carried out continuously or batchwise.
For example, the olefin or a mixture of different olefins may be initially taken in the reactor and heated to the desired polymerization temperature while stirring. As soon as the olefin has reached the polymerization tem-perature, the ethylenically unsaturated dicarboxylicanhydride is metered in. If an initiator is used, it is metered into the reaction mixture preferably separately or in solution in an olefin used for the polymerization.
Where it is used, the polymerization regulator is addPd to the polymerization mixture eithex separately or liXewise in solution in an olefin. Anhydrides, in particular maleic anhydride, are preferably added in the form of a melt to the reaction mixture. The temperature of the melt is about 70-90C. If, in the copolymeriza-tion, the olefin i5 used in excess) for example in a 10%excess, it can be removed from the reaction mixture without difficulties after the end of the copolymeriza-tion, by means of distilla~ion, preferably under reduced pressure, from the copolymer melt. The copolymer melt is then advantageously directly fur~her processed.
The copolymer~ prepared in this manner are sub~ected to solvolysis after cooling to room temperature - 6 - O.Z. 0050/41004 or preferably in the form of a melt which is from 80 to 180C, preferably from 90 to 150C. Solvolysis of the anhydride groups of the copolymers consist inthe simplest case in hydrolysis and subsequent neutralization. It is particularly advantageous to carry out the procedure in pressure-resistant apparatuses and to convert the anhyd-ride group~ into carboxyl group~ therein directly by the addition of water to a melt of the copolymers obtainable in the mass polymerization, and to neutralize not less than 10% of the carboxyl groups of the hydrolyzed copoly-mers by subsequent addition of a base. Hydrolysis and neutralization can, however, also be carried out virtu-ally simultaneously by the addition of a dilute aqueous base to the copolymer melt. The amounts of water and neutralizing ag~nt are chosen to give solutions or dispersions which have a solids content of from 10 to 60, preferably from 20 to 55, % by weight and are made commercially available. These are then converted into preparation solutions by dilution to solids contents of from 0.5 to 50~ by weight.
The copolymers obtainable by ma~s polymerization can also be subjected to solvolysis by the addition of primary and/or secondary amine~. Solvolysis is carried out using amounts of amines such that from 10 to 50% of the total amount o~ carboxyl groups formed from the polymerized monomer3 (b) in the event of complete hydrol-y3i~ undergo amidation. After the formation of the semi-amide group~ in the copol~mer, neutralization is carried out. It i continued until not les~ than 10% of the carboxyl groups of the copolymer obtained in the mass polymerization are neutralized. Furthermore, solvolysis may also be carried out u~ing aminocarboxylic acids and salts of aminocarboxylic acids, preferably the alkali metal salt~. Alkali metal salts of ~-aminocarboxylic acids are particularly preferably used, the alkali metal ; salts of sarcosine being very particularly advantageous.
Solvolysis by means of salt~ of aminocarboxylic acids is - 7 - O.Z. 0050/4100~
advantageously carried out in an aqueous medium. Sol-volysis is effected u~ing amounts of aminocarboxylates such that from 10 to 50% of the total amount of carboxyl groups formed from the polymerized monomers (b) in the S event of complete hydrolysis undergo amidation. After the formation of the qemi-amide groups in the copolymer, neutralization i8 carried out. It i5 continued until not less than 10% of the carboxyl groups of the copolymer obtained in the mass polymerization are neutralized.
Solvolysis can also be carried out by adding alcohols to a melt of the copolymers obtainable by mass polymerization. The amounts of alcohol used are such that from 10 to 50% of the total amount of carboxyl groups formed from the polymerized dicarboxylic acid units are esterified. Neutralization i~ subsequently effected, in which not less than 10% of the total amount of carboxyl group~ formed from the anhydride-containing copolymer are neutralized.
Preferably, in each case fxom 25 to 50% of the total amount of carboxyl groups formed from the polymer-ized dicarboxylic anhydride~ undergo amidation or ester-ification. Examples of suitable neutralizing agent3 re ammonia, amine~, alkali metal and alkaline earth metal bases, for example sodium hydroxide solution, pota~sium hydroxide solution, magne~ium hydroxide, calcium hydrox-ide, barium hydroxidQ and all amines which are also used for amidation of the copolymers. Neutralization i~
prefexably effected by adding aqueous sodium hydroxide solution to the copolymer. The neutraliæation of the anhydride-containing copolymer~ is carried out at least to a degree ~uch that water-di~persible copolymer~ are obtained. This degree of neutralization is not le~ than 10% of the total amount of carboxyl group formed from the anhydride groups. The degrea of neutralization is furthermore dependent on the chain length of the particu-lar olefin of component (a) u~ed. In order to obtain copolymers which ara readily water dispersible or soluble 2 o 2 1 r~
- 8 - O.Z. 0050/41004 to give a colloidal solution, a copolymer of a C30-olefin and maleic anhydride is subjected to not less than 75%
nautralization, whereas, for example, acopolymer obtained from a C20/C24-olefin and maleic anhydride i5 readily water dispersible when the degree of neutralization corresponds to 50~ of the carboxyl groups formed from this copolymer.
In a copolymer obtained from a Cl2-olefin and maleic an-hydride, a degree of neutralization of only 20% of the carboxyl groups formed from ths polymerized maleic anhydride is sufficient for dispersing the copolymer in water.
For ~mide formation, ammonia and primary and secondary amlnes may be used. Amide formation is prefer-ably effected in the absence of water by reaction of the anhydride groups of the copolymer with ammonia or amines.
The suitable prLmary and secondary amines may contain 1 to 40, preferably 3 to 30, carbon atoms. Examples of suitable amines are methylamine, ethylamine, n-propyl-amine, isopropylamine, n-butylamine, isobutylamine, hexylamine, cyclohexylamine, methylcyclohexylamine, 2-ethylhexylamine, n-octylamine, isotridecylamine, tallow fatty amine, stearylamine, oleylamine, dLmethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, dihexylamine, dicyclohexyl-amine, dimethylcyclohexylamin~, di-2-ethylhexylamine, di-n-octylamine, diisotridecylamine, di-tallow fatty amine, distearylamine, dioleylamine, ethanolamine, diethanol-amine, n~propanolamine, di-n-propanolamine and morpho-line. Morpholine i3 preferably used.
In vrder to effect partial e~terification of the anhydride-containing copolymer~ obtained in the ma~s polymerization, the said polymer~ are reacted with alcohols. The e3terification is al~o preferably carried out in the absence of water. Suitable alcohol3 may con-tain 1 to 40, preferably 3 to 30, carbon atom3. Primary, secondary and tertiary alcohols may be used. Both saturated aliphatic alcohols and unsaturated alcohols, .
r~
- 9 - O. Z . 0050/41û04 for example oleyl alcohol, may be employed. ~onohydric, primary or secondary alcohols are preferably used, for example methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol and isomers, n-hexanol S and isomers, n-octanol and isomers, such as 2-ethyl-hexanol, nonanols, decanols, dodecanols, tridecanol~, cyclohexanol, tallow fatty alcohol, stearyl alcohol and the alcohols and alcohol mixture~ of 9 to 19 carbon atoms which are readily obtainable industrially by the oxo pro-cess, for example Cg/ll oxo alcohol, Cl3tl5 oxo alcohol and Ziegler alcohols of 12 to 24 carbon atoms, which are known under the name Alfol. Alcohols of 4 to 24 carbon atoms, eg. n-butanol, isobutanol, amyl alcohol, 2-ethyl-hexanol, tridecanol, tallow fatty alcohol, stearyl alco-lS hol, Cg/ll oxo alcohol, Cl3/15 oxo alcohol, C12/l4 Alfols and Cl6/l8 ~lfols, are preferably used.
After the partial conversion of the anhydride groups into semi-amide or half-ester groups, hydrolysis of the remaining anhydride groups of the copolymer is carried out. The hydrolysis of the remaining anhydride group~ of the copolymer may also be carried out sLmul-taneously with the partial neutralization still required, by adding an aqueous base to the partially amidated or esterified copolymer still containing anhydride group~.
The amount of water and ba~e~ is cho~en so that the con-centration of the copolymer di~persion or solution i3 - preferably from 20 to 55% by weightO The p~ of the ready~to-use agent for imparting water-repellancy i5 about 4-10.
The aqueous copolymer dispersions thus obtainable are stable and have a long ~helf life. They ara very - suitable for finishing leathers and ~kins because they have a particularly pronounoed action in imparting water-repellency and moreover have a fatliquoring and retanning action. The leather and skin material treated with these copolymex di~per~ion~ exhibit~ only little water ab~orp-tivity and water perMeability. The disper~ions 2~2~ 7~8 - 10 - O.Z. 0050/41004 simultaneously act as plasticizers, so that in most cases no additional fatliquoring agents based on natural or synthetic fatliquoring oils are required. The disper-sions impart to the product good body and high tensile strength and tear strength, so that additional treatment with commercial retanning a~ents, for example with vege-table tanning agents or synthetic organic tanning agents (syntans)basedonphenolsulfonic acid/phenol/formaldehyde condensates, is no longer necessary in most cases.
1~ Another advantage of the aqueous dispersions to be used according to the invention is that they contain no additional emulsifiers. It is known that leathers and - skins which have been treated with emulsifier-containing products must, after treatment with these agents, be sub-jected to expensive processes, for example aftertreatment with polyvalent metal salts, in order to deactivate the emulsifiers in the leather or in the skins.
The copolymer dispersions or copolymer solutions described above are suitable for the treatment of all conventional tanned hides, in particular hides tanned with mineral tanning agents, such a~ chromium(III) ~alts.
The tanned hides are usually neutralized before the treatment. They may be dyed before the treatment. How-ever, dyeing may also be carried out after the water-repellent treatment ef~ected according to the invention.
The tanned hides are treated with the aqueous dispersion~ advantayeously in an agueous liquor ob~ain-able by diluting the copol~mer dispersions with water, at a p~ of from 4 to lO, preferably from 5 to 8, and at from 20 to 60C, preferably from 30 to 50C, for from 0.1 to 5, in particulax from 0.5 to 2, hour~. This treatment is effected, for example, by drumming. The required amount of copolymar dispersion is from 0.1 to 30, preferably from 1 to 20, % by weight, based on the shaved weight of the leather or the wet weight of the skin. The liquor length, ie. the percentage weight ratio of treatment liquor to goods, based on the ~haved weight of the 7 ~ ~
~ O.Z. 0050/41004 leather or the wet weight of the skin, i5 usually from 10 to 1000%, preferably from 30 to 150%, or from 50 to 500%
in the case of skins.
After the treatment with the aqueous liquor des-cribed above, the pH of the treatment liquor is brought to 3-5, preferably 3.5-4, by the addition of an acid;
organic acids, such as formic acid, are preferably used.
When conventional retanning agent~ are present during finishing of the leather and of the skin, the treatment with the aqueous dispersions or solutions to be used according to the invention can be carried out before or after the retanning step or as a multistage proces3, the aqueous dispersions being used proportionately before, during and after the retanning ~tep. The aqueouq dispersions to be used as water-repellents may also be employed together with conventional leather and skin finishing agents, such as paraffin-based water-repellent fatliquors. In some case~, this improves the water-repellent, fatliquoring and retanning effect.
In the Example~, percentages are by weight, unless stated otherwise. The molecular weights of the copolymers were determined by gel permeation chromatog-raphy, tetrahydrofuran being used a3 the eluent and poly-styrene fraction~ having a narrow di~tribution being u~ed for calibration. The treated leathers werP tested for water absorptivity and water permeability u~ing a Bally penetrometer according to mea~urement me~hod IUP 10 of the International Union cf the Leather Chemi~t~ A~socia-tions, Commi~sions for Physical Leather Testing, cf. das Leder, 12 (1961), 36-40.
Preparation of aqueou~ copolymer dispersion~
Dispersion I
In a ~teel reactor equipped for polymerization~
and provided with a s~irrer and metering apparatuses, 1195 g of a l-(C20-C24-olefin) mixture ~Gulftene 20-24, commercial product from Gulf Oil Chemical Company, USA) are initially taken and heated to 190C in a gentle stream - 12 - O.Z. 0050/41004 of nitrogen, while stirring. As soon as this temperature has been reached, 392 g of maleic anhydride, heated to 70C, are added uniformly and, separately from this, 16 g of di-tert-butyl peroxide are introduced in the course of 4 hours. Thereafter, the reaction mixture is stirred for 2 hours at 190C and cooled to 90C while stirring. 320 g of 50~ strength sodium hydroxide solution and 3909 g of water heated to 90C are then added in the course of half an hour, separately from one another. The reaction mix-ture is stirred for 4 hours at from 90 to 95CC and then cooled to ambient temperature. This gives a slightly viscous aqueous dispersion having a solids content of 30.2%. The molecular weight of the nonhydrolyzed copoly-mer of olefin and maleic anhydride is 8900 g/mol, 50 mol % of the total amount of carboxyl groups formed having been neutralized.
Dispersion II
In the reactor in which dispersion I is prepared, 1500 g of octadec-l-ene are initially taken and heated to 190C in a nitrogen atmosphere, while stirring. As soon as this temperature has been reached, 588 g o~ a melt of maleic anhydride and a solution of 27 g of di-tert-butyl peroxide in 42.8 g of octadec-l-ene are each added in tha course of 2 hours, separately from one another. After ~ 25 the addition of the maleic anhydride and of the p~roxide, - the reaction mixture is heated for a further 2 hours at 190C and then cooled to 110C. Thereafter, 522 g of morpholine are metexed in over 1 hour. The reaction temperature is kept at 110C. After the end of the mor-pholine addition, the reaction mixture is stirred for a further 2 hours at 110C in order to convert the an-hydride groups of the copolymer into the corresponding semi-amide groups. The stirred r~action mixture i~ then - cooled to 90C and 480 g of 50% strength aqueous hydrox-ide solution and &680 g of water at 90C are added in the course of half an hour, separately from one another, and the mix~ure is heated for a further 2 hours at 90C. This 2~32~ri~r~
- 13 - O.Z. ~050/41004 gives a dispersion which is viscous at room temperature and has a solids content of 25.4%. The molecular weight of the nonsolvolyzed copolymer is 4800 g/mol, 50 mol % of the total amount of carboxyl groups formed from the anhydride groups being present as amide groups and 50 mol being present in neutralized form.
Chrome-tanned ox leather which had a shaved thickness of 1.8 mm and had been brought to a pH of 5.0 was drummed for 2 hours at 40C with 15~, based on shaved weight, of dispersion I. The total liquor length was 150%.
Thereafter, the leather was dyed with 1% by weight of a conventional anionic aniline dye. It wa3 then brought to a pH of 3.8 with formic acidt after which it was washed, mechanically set out and dried.
The leather obtainad was very soft and supple, had good body, was uniformly dyed and exhibited excellent dynamic water resistance. The test using the Bally penetrometer gave a value of 20.9% for the water ab~orp-tion after 24 hours at 15% compression and did not indicate any water permeability at this time.
Chrome-tanned ox leather which had a shaved thickness of 1.8 mm and had been brought to a pH of 5.O
and dyed with 0.7% by weight of a conventional aniline dye wa~ drummed for one and a half hour-~ at 40C with 20%
; of dispersion II, the percentage being based on the shaved weight. After this treatment, the leather wa~
brought to a pH of 3.6 with formic acid and was fini~hed in a eonventional manner.
The leather obtained was very soft and supple and exhibited high dynamic water resistance. The te~t with the Bally penetrometer gave a value of 23.7~ for the water absorption after 24 hours ~t 15% compression and did not indicate any water permeability during this time.
.
They are obtainable by polymerization of the monomers (a) and (b) in a molar ratio of from 1.1 : 1 to 1 : 1. The monomers (a) and (,b) are preferably polymerized in a molar ratio of 1 : 1 or only a 1~ by weight excess of monomers of component (a) is used. The monomers of groups (a) and (b) are known to foxm alternating copoly-mers which, in the case of high molecular weights, contain 50 mol % of monomers (a) and 50 mol % of monomers (b) as polymerized units. In the case of very low molecular weights of the copolymers, the molar ratio may differ from the abovementioned range, depending on the type of terminal groups, if, for example, the copolymer chain star~s with the monomers ~a) and also ends with the monomers (a).
Mass polymerization is carried out at from 80 to 300C, preferably from 120 to 200C, the lowest polymerization temperature chosen preferably being at least about 20C above the glass transition temperature of the polymer formed. The polymerization condition~ are chosen according to the desired molecular weight of the copolymers. Polymerization at high temperatures gives copolymers having low molecular weight~ whereas polymers having higher molecular weights ar~ formed at lower poly-merization temperatures. The amount of polymerization initiator also has an effect on the molecular weight. In general, from 0.01 to 5~ by weight, based on the monomers used in the polymerization, of free radical polymeriza-tion initiators are required. Larger ~mounts of initia-~or lead to copolymers having lower molecular weights.
At above 200C, the monomer~ la) and (b) can also be copolymerized in the absence of polymerization initia-tors, ie. it is not absolutely e~sential to use initia-tors, because the monnmer~ (a) and tb~ undergo free -2~2~
- ~ - O.Z. 0050/41004 radical polymerization also in the absence of initiators at above 200C. Examples of suitable polymerization initiators are di-tert-butyl peroxide, acetylcyclohexane-sulfonyl peroxide, diacetyl peroxydicarbonate, dicyclo-hexyl peroxydicarbonate, di-2-ethylhexyl peroxydi-carbonate, tert-butyl perneodecanoate, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile)~ tert-butyl perpiva-late, tert-butyl per-2-ethylhexanoate, tert-bukyl per-maleate, 2,2'-azobisisobutyronitrile, bis-(tert-butyl-peroxy)-cyclohexane,tert-butylperoxyisopropylcarbonate, tert-butyl peracetate, di-tert-butyl peroxide, di-tert-amyl peroxide, cumene hydroperoxide and tert-butyl hydroperoxide. The initiators can be used alone or as a mixture with one another. In mass polymerization, they are preferably introduced into the polymerization reactor separately or in the form of a solution or dispersion in the monoolefin. In ~he copolymerization, it is of course also possible to use redox coini~iators, for example benzoin, dimethylaniline, ascorbic acid and complexes of heavy metals, such as copper, cobalt, iron, manganese, nickel and chromium, which complexes are soluble in organic solvents. The presence of redox coinitiators permits the polymerization to be carried out at lower temperatures. The amounts of redox coinitiator~ usually ; 25 used are about 0.1-2000 ppm, preferably 0.1-1000 ppm, based on the amount~ o monomers ~lsed. If the monomer mixture ic initially polymerized at the lower limit of the temperature range suitable for the polymerization and then completely polymerized at a higher temperature, it is advantageou~ to u~e twc or more different initiators which decompose at different temperatures, so that a sufficient concentration o free radicals i5 a~ailabl.9 within each temperature range.
In order to prepare low molecular weight poly-mer~, it is often advantageou~ to carry out ~he copoly-merization in the presence of regulator Conventional regulators may be used for thi~ purpose, for example 2 0 ~
- 5 - O.Z. 0050/41004 Cl-C4-aldehydes, ormic acid a~d compound~ containing or-ganic SH groups, such as 2-mercaptoethanol, 2-mercapto-propanol, mercaptoacetic acid, mercaptopropionic acid, tert-butyl mercaptan, n-dodecyl mercaptan and tert-dodecyl mercaptan. Polymerizatlon regulators are gener-ally used in amounts of from 0.1 to 10% by weight, based on the monomers.
The copolymerization is carried out in conven-tionalpolymerization apparatuses, for example a pressure-resistant kettle which is provided with a stirrer, in pressure-resistant stirred kettle cascades or in a tubular reactor. In the case of mass polymerization, the olefins and the anhydrides are copolymerized in an equi-molar ratio in the absence of solvents. The copoly-merization can be carried out continuously or batchwise.
For example, the olefin or a mixture of different olefins may be initially taken in the reactor and heated to the desired polymerization temperature while stirring. As soon as the olefin has reached the polymerization tem-perature, the ethylenically unsaturated dicarboxylicanhydride is metered in. If an initiator is used, it is metered into the reaction mixture preferably separately or in solution in an olefin used for the polymerization.
Where it is used, the polymerization regulator is addPd to the polymerization mixture eithex separately or liXewise in solution in an olefin. Anhydrides, in particular maleic anhydride, are preferably added in the form of a melt to the reaction mixture. The temperature of the melt is about 70-90C. If, in the copolymeriza-tion, the olefin i5 used in excess) for example in a 10%excess, it can be removed from the reaction mixture without difficulties after the end of the copolymeriza-tion, by means of distilla~ion, preferably under reduced pressure, from the copolymer melt. The copolymer melt is then advantageously directly fur~her processed.
The copolymer~ prepared in this manner are sub~ected to solvolysis after cooling to room temperature - 6 - O.Z. 0050/41004 or preferably in the form of a melt which is from 80 to 180C, preferably from 90 to 150C. Solvolysis of the anhydride groups of the copolymers consist inthe simplest case in hydrolysis and subsequent neutralization. It is particularly advantageous to carry out the procedure in pressure-resistant apparatuses and to convert the anhyd-ride group~ into carboxyl group~ therein directly by the addition of water to a melt of the copolymers obtainable in the mass polymerization, and to neutralize not less than 10% of the carboxyl groups of the hydrolyzed copoly-mers by subsequent addition of a base. Hydrolysis and neutralization can, however, also be carried out virtu-ally simultaneously by the addition of a dilute aqueous base to the copolymer melt. The amounts of water and neutralizing ag~nt are chosen to give solutions or dispersions which have a solids content of from 10 to 60, preferably from 20 to 55, % by weight and are made commercially available. These are then converted into preparation solutions by dilution to solids contents of from 0.5 to 50~ by weight.
The copolymers obtainable by ma~s polymerization can also be subjected to solvolysis by the addition of primary and/or secondary amine~. Solvolysis is carried out using amounts of amines such that from 10 to 50% of the total amount o~ carboxyl groups formed from the polymerized monomer3 (b) in the event of complete hydrol-y3i~ undergo amidation. After the formation of the semi-amide group~ in the copol~mer, neutralization is carried out. It i continued until not les~ than 10% of the carboxyl groups of the copolymer obtained in the mass polymerization are neutralized. Furthermore, solvolysis may also be carried out u~ing aminocarboxylic acids and salts of aminocarboxylic acids, preferably the alkali metal salt~. Alkali metal salts of ~-aminocarboxylic acids are particularly preferably used, the alkali metal ; salts of sarcosine being very particularly advantageous.
Solvolysis by means of salt~ of aminocarboxylic acids is - 7 - O.Z. 0050/4100~
advantageously carried out in an aqueous medium. Sol-volysis is effected u~ing amounts of aminocarboxylates such that from 10 to 50% of the total amount of carboxyl groups formed from the polymerized monomers (b) in the S event of complete hydrolysis undergo amidation. After the formation of the qemi-amide groups in the copolymer, neutralization i8 carried out. It i5 continued until not less than 10% of the carboxyl groups of the copolymer obtained in the mass polymerization are neutralized.
Solvolysis can also be carried out by adding alcohols to a melt of the copolymers obtainable by mass polymerization. The amounts of alcohol used are such that from 10 to 50% of the total amount of carboxyl groups formed from the polymerized dicarboxylic acid units are esterified. Neutralization i~ subsequently effected, in which not less than 10% of the total amount of carboxyl group~ formed from the anhydride-containing copolymer are neutralized.
Preferably, in each case fxom 25 to 50% of the total amount of carboxyl groups formed from the polymer-ized dicarboxylic anhydride~ undergo amidation or ester-ification. Examples of suitable neutralizing agent3 re ammonia, amine~, alkali metal and alkaline earth metal bases, for example sodium hydroxide solution, pota~sium hydroxide solution, magne~ium hydroxide, calcium hydrox-ide, barium hydroxidQ and all amines which are also used for amidation of the copolymers. Neutralization i~
prefexably effected by adding aqueous sodium hydroxide solution to the copolymer. The neutraliæation of the anhydride-containing copolymer~ is carried out at least to a degree ~uch that water-di~persible copolymer~ are obtained. This degree of neutralization is not le~ than 10% of the total amount of carboxyl group formed from the anhydride groups. The degrea of neutralization is furthermore dependent on the chain length of the particu-lar olefin of component (a) u~ed. In order to obtain copolymers which ara readily water dispersible or soluble 2 o 2 1 r~
- 8 - O.Z. 0050/41004 to give a colloidal solution, a copolymer of a C30-olefin and maleic anhydride is subjected to not less than 75%
nautralization, whereas, for example, acopolymer obtained from a C20/C24-olefin and maleic anhydride i5 readily water dispersible when the degree of neutralization corresponds to 50~ of the carboxyl groups formed from this copolymer.
In a copolymer obtained from a Cl2-olefin and maleic an-hydride, a degree of neutralization of only 20% of the carboxyl groups formed from ths polymerized maleic anhydride is sufficient for dispersing the copolymer in water.
For ~mide formation, ammonia and primary and secondary amlnes may be used. Amide formation is prefer-ably effected in the absence of water by reaction of the anhydride groups of the copolymer with ammonia or amines.
The suitable prLmary and secondary amines may contain 1 to 40, preferably 3 to 30, carbon atoms. Examples of suitable amines are methylamine, ethylamine, n-propyl-amine, isopropylamine, n-butylamine, isobutylamine, hexylamine, cyclohexylamine, methylcyclohexylamine, 2-ethylhexylamine, n-octylamine, isotridecylamine, tallow fatty amine, stearylamine, oleylamine, dLmethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, dihexylamine, dicyclohexyl-amine, dimethylcyclohexylamin~, di-2-ethylhexylamine, di-n-octylamine, diisotridecylamine, di-tallow fatty amine, distearylamine, dioleylamine, ethanolamine, diethanol-amine, n~propanolamine, di-n-propanolamine and morpho-line. Morpholine i3 preferably used.
In vrder to effect partial e~terification of the anhydride-containing copolymer~ obtained in the ma~s polymerization, the said polymer~ are reacted with alcohols. The e3terification is al~o preferably carried out in the absence of water. Suitable alcohol3 may con-tain 1 to 40, preferably 3 to 30, carbon atom3. Primary, secondary and tertiary alcohols may be used. Both saturated aliphatic alcohols and unsaturated alcohols, .
r~
- 9 - O. Z . 0050/41û04 for example oleyl alcohol, may be employed. ~onohydric, primary or secondary alcohols are preferably used, for example methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol and isomers, n-hexanol S and isomers, n-octanol and isomers, such as 2-ethyl-hexanol, nonanols, decanols, dodecanols, tridecanol~, cyclohexanol, tallow fatty alcohol, stearyl alcohol and the alcohols and alcohol mixture~ of 9 to 19 carbon atoms which are readily obtainable industrially by the oxo pro-cess, for example Cg/ll oxo alcohol, Cl3tl5 oxo alcohol and Ziegler alcohols of 12 to 24 carbon atoms, which are known under the name Alfol. Alcohols of 4 to 24 carbon atoms, eg. n-butanol, isobutanol, amyl alcohol, 2-ethyl-hexanol, tridecanol, tallow fatty alcohol, stearyl alco-lS hol, Cg/ll oxo alcohol, Cl3/15 oxo alcohol, C12/l4 Alfols and Cl6/l8 ~lfols, are preferably used.
After the partial conversion of the anhydride groups into semi-amide or half-ester groups, hydrolysis of the remaining anhydride groups of the copolymer is carried out. The hydrolysis of the remaining anhydride group~ of the copolymer may also be carried out sLmul-taneously with the partial neutralization still required, by adding an aqueous base to the partially amidated or esterified copolymer still containing anhydride group~.
The amount of water and ba~e~ is cho~en so that the con-centration of the copolymer di~persion or solution i3 - preferably from 20 to 55% by weightO The p~ of the ready~to-use agent for imparting water-repellancy i5 about 4-10.
The aqueous copolymer dispersions thus obtainable are stable and have a long ~helf life. They ara very - suitable for finishing leathers and ~kins because they have a particularly pronounoed action in imparting water-repellency and moreover have a fatliquoring and retanning action. The leather and skin material treated with these copolymex di~per~ion~ exhibit~ only little water ab~orp-tivity and water perMeability. The disper~ions 2~2~ 7~8 - 10 - O.Z. 0050/41004 simultaneously act as plasticizers, so that in most cases no additional fatliquoring agents based on natural or synthetic fatliquoring oils are required. The disper-sions impart to the product good body and high tensile strength and tear strength, so that additional treatment with commercial retanning a~ents, for example with vege-table tanning agents or synthetic organic tanning agents (syntans)basedonphenolsulfonic acid/phenol/formaldehyde condensates, is no longer necessary in most cases.
1~ Another advantage of the aqueous dispersions to be used according to the invention is that they contain no additional emulsifiers. It is known that leathers and - skins which have been treated with emulsifier-containing products must, after treatment with these agents, be sub-jected to expensive processes, for example aftertreatment with polyvalent metal salts, in order to deactivate the emulsifiers in the leather or in the skins.
The copolymer dispersions or copolymer solutions described above are suitable for the treatment of all conventional tanned hides, in particular hides tanned with mineral tanning agents, such a~ chromium(III) ~alts.
The tanned hides are usually neutralized before the treatment. They may be dyed before the treatment. How-ever, dyeing may also be carried out after the water-repellent treatment ef~ected according to the invention.
The tanned hides are treated with the aqueous dispersion~ advantayeously in an agueous liquor ob~ain-able by diluting the copol~mer dispersions with water, at a p~ of from 4 to lO, preferably from 5 to 8, and at from 20 to 60C, preferably from 30 to 50C, for from 0.1 to 5, in particulax from 0.5 to 2, hour~. This treatment is effected, for example, by drumming. The required amount of copolymar dispersion is from 0.1 to 30, preferably from 1 to 20, % by weight, based on the shaved weight of the leather or the wet weight of the skin. The liquor length, ie. the percentage weight ratio of treatment liquor to goods, based on the ~haved weight of the 7 ~ ~
~ O.Z. 0050/41004 leather or the wet weight of the skin, i5 usually from 10 to 1000%, preferably from 30 to 150%, or from 50 to 500%
in the case of skins.
After the treatment with the aqueous liquor des-cribed above, the pH of the treatment liquor is brought to 3-5, preferably 3.5-4, by the addition of an acid;
organic acids, such as formic acid, are preferably used.
When conventional retanning agent~ are present during finishing of the leather and of the skin, the treatment with the aqueous dispersions or solutions to be used according to the invention can be carried out before or after the retanning step or as a multistage proces3, the aqueous dispersions being used proportionately before, during and after the retanning ~tep. The aqueouq dispersions to be used as water-repellents may also be employed together with conventional leather and skin finishing agents, such as paraffin-based water-repellent fatliquors. In some case~, this improves the water-repellent, fatliquoring and retanning effect.
In the Example~, percentages are by weight, unless stated otherwise. The molecular weights of the copolymers were determined by gel permeation chromatog-raphy, tetrahydrofuran being used a3 the eluent and poly-styrene fraction~ having a narrow di~tribution being u~ed for calibration. The treated leathers werP tested for water absorptivity and water permeability u~ing a Bally penetrometer according to mea~urement me~hod IUP 10 of the International Union cf the Leather Chemi~t~ A~socia-tions, Commi~sions for Physical Leather Testing, cf. das Leder, 12 (1961), 36-40.
Preparation of aqueou~ copolymer dispersion~
Dispersion I
In a ~teel reactor equipped for polymerization~
and provided with a s~irrer and metering apparatuses, 1195 g of a l-(C20-C24-olefin) mixture ~Gulftene 20-24, commercial product from Gulf Oil Chemical Company, USA) are initially taken and heated to 190C in a gentle stream - 12 - O.Z. 0050/41004 of nitrogen, while stirring. As soon as this temperature has been reached, 392 g of maleic anhydride, heated to 70C, are added uniformly and, separately from this, 16 g of di-tert-butyl peroxide are introduced in the course of 4 hours. Thereafter, the reaction mixture is stirred for 2 hours at 190C and cooled to 90C while stirring. 320 g of 50~ strength sodium hydroxide solution and 3909 g of water heated to 90C are then added in the course of half an hour, separately from one another. The reaction mix-ture is stirred for 4 hours at from 90 to 95CC and then cooled to ambient temperature. This gives a slightly viscous aqueous dispersion having a solids content of 30.2%. The molecular weight of the nonhydrolyzed copoly-mer of olefin and maleic anhydride is 8900 g/mol, 50 mol % of the total amount of carboxyl groups formed having been neutralized.
Dispersion II
In the reactor in which dispersion I is prepared, 1500 g of octadec-l-ene are initially taken and heated to 190C in a nitrogen atmosphere, while stirring. As soon as this temperature has been reached, 588 g o~ a melt of maleic anhydride and a solution of 27 g of di-tert-butyl peroxide in 42.8 g of octadec-l-ene are each added in tha course of 2 hours, separately from one another. After ~ 25 the addition of the maleic anhydride and of the p~roxide, - the reaction mixture is heated for a further 2 hours at 190C and then cooled to 110C. Thereafter, 522 g of morpholine are metexed in over 1 hour. The reaction temperature is kept at 110C. After the end of the mor-pholine addition, the reaction mixture is stirred for a further 2 hours at 110C in order to convert the an-hydride groups of the copolymer into the corresponding semi-amide groups. The stirred r~action mixture i~ then - cooled to 90C and 480 g of 50% strength aqueous hydrox-ide solution and &680 g of water at 90C are added in the course of half an hour, separately from one another, and the mix~ure is heated for a further 2 hours at 90C. This 2~32~ri~r~
- 13 - O.Z. ~050/41004 gives a dispersion which is viscous at room temperature and has a solids content of 25.4%. The molecular weight of the nonsolvolyzed copolymer is 4800 g/mol, 50 mol % of the total amount of carboxyl groups formed from the anhydride groups being present as amide groups and 50 mol being present in neutralized form.
Chrome-tanned ox leather which had a shaved thickness of 1.8 mm and had been brought to a pH of 5.0 was drummed for 2 hours at 40C with 15~, based on shaved weight, of dispersion I. The total liquor length was 150%.
Thereafter, the leather was dyed with 1% by weight of a conventional anionic aniline dye. It wa3 then brought to a pH of 3.8 with formic acidt after which it was washed, mechanically set out and dried.
The leather obtainad was very soft and supple, had good body, was uniformly dyed and exhibited excellent dynamic water resistance. The test using the Bally penetrometer gave a value of 20.9% for the water ab~orp-tion after 24 hours at 15% compression and did not indicate any water permeability at this time.
Chrome-tanned ox leather which had a shaved thickness of 1.8 mm and had been brought to a pH of 5.O
and dyed with 0.7% by weight of a conventional aniline dye wa~ drummed for one and a half hour-~ at 40C with 20%
; of dispersion II, the percentage being based on the shaved weight. After this treatment, the leather wa~
brought to a pH of 3.6 with formic acid and was fini~hed in a eonventional manner.
The leather obtained was very soft and supple and exhibited high dynamic water resistance. The te~t with the Bally penetrometer gave a value of 23.7~ for the water absorption after 24 hours ~t 15% compression and did not indicate any water permeability during this time.
.
Claims (5)
1. A process for rendering leathers and skins water-repellent, wherein water-repellency is imparted using a copolymer which is obtainable by free radical copolymer-ization of (a) C8-C40-monoolefins with (b) ethylenically unsaturated C4-C8-dicarboxylic anhyd-rides, by a mass polymerization method at from 80 to 300°C, to give a copolymer having a molecular weight of from 500 to 20,000 g/mol, subsequent solvolysis of the anhydride groups of the copolymer and partial or complete neutral-ization of the carboxyl groups formed during the solvol-ysis, in an aqueous medium by means of a base, and which is present in the form of an aqueous solution or dispersion.
2. A process as claimed in claim 1, wherein the solvolysis is carried out by adding water to a melt of the copolymer obtainable in the mass polymerization, and not less than 10% of the carboxyl groups of the hydrol-yzed copolymer are neutralized with ammonia, an amine or an alkali metal or alkaline earth metal base.
3. A process as claimed in claim 1, wherein the sol-volysis is carried out by adding primary and/or secondary amines to a melt of the copolymer obtainable in the mass polymerization, in such a way that from 10 to 50% of the total amount of carboxyl groups formed from the polymer-ized monomers (b) undergo amidation and not less than 10%
of the total amount of carboxyl groups formed are neutralized.
of the total amount of carboxyl groups formed are neutralized.
4. A process as claimed in claim 1, wherein the solvolysis of the copolymer obtainable in the mass polymerization is carried out in an aqueous medium by adding a salt of an aminocarboxylic acid, in such a way that from 10 to 50% of the total amount of carboxyl groups formed from the polymerized monomers (b) undergo amidation and not less than 10% of the total amount of - 15 - O.Z. 0050/41004 carboxyl groups formed are neutralized.
5. A process as claimed in claim 1, wherein the solvolysis is carried out by adding an alcohol to a melt of the copolymer obtainable in the mass polymerization, in such a way that from 10 to 50% of the total amount of carboxyl groups formed from the polymerized monomers (b) are esterified and not less than 10% of the total amount of carboxyl groups formed are neutralized.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3926167A DE3926167A1 (en) | 1989-08-08 | 1989-08-08 | USE OF COPOLYMERISATS BASED ON LONG-CHAIN OLEFINS AND ETHYLENICALLY UNSATURATED DICARBONIC ACID ANHYDRIDES FOR THE HYDROPHOBICATION OF LEATHER AND FUR SKINS |
| DEP3926167.0 | 1989-08-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2021758A1 true CA2021758A1 (en) | 1991-02-09 |
Family
ID=6386714
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002021758A Abandoned CA2021758A1 (en) | 1989-08-08 | 1990-07-23 | Use of copolymers based on long-chain olefins and ethylenically unsaturated dicarboxylic anhydrides for rendering leathers and skins water-repellent |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0412389B1 (en) |
| JP (1) | JPH0376800A (en) |
| KR (1) | KR910004817A (en) |
| AT (1) | ATE114727T1 (en) |
| AU (1) | AU628205B2 (en) |
| CA (1) | CA2021758A1 (en) |
| DE (2) | DE3926167A1 (en) |
| ES (1) | ES2064554T3 (en) |
| NZ (1) | NZ234781A (en) |
| PT (1) | PT94915B (en) |
Families Citing this family (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4129244A1 (en) * | 1991-09-03 | 1993-03-04 | Henkel Kgaa | AQUEOUS DISPERSIONS OF NEW AMPHIPHILE CO-OLIGOMERS FOR THE WASHING AND CLEANING-RESISTANT FATTY EQUIPMENT OF LEATHER AND FUR SKINS AND THEIR USE |
| DE4133123A1 (en) * | 1991-10-05 | 1993-04-08 | Basf Ag | USE OF COPOLYMERISATES FROM LONG-CHAIN OLEFINS AND MALEINIC ACID ANHYDRIDE IN THE FORM OF HALBAMIDES WITH MORPHOLINE AS A SIZING AGENT FOR PAPER |
| DE4137476A1 (en) * | 1991-11-14 | 1993-05-19 | Basf Ag | USE OF PIGMENT PREPARATIONS FOR THE PRODUCTION OF PASTE, PRINTING INKS AND VARNISHES |
| DE4139090A1 (en) * | 1991-11-28 | 1993-06-03 | Stockhausen Chem Fab Gmbh | USE OF COPOLYMERS WITH POLYSILOXANE UNITS FOR THE TREATMENT OF LEATHER AND FURS |
| US5268437A (en) * | 1992-01-22 | 1993-12-07 | Rohm And Haas Company | High temperature aqueous polymerization process |
| DE4205839A1 (en) * | 1992-02-26 | 1993-09-02 | Basf Ag | USE OF IMPLEMENTATION PRODUCTS OF HOMO OR COPOLYMERISATS BASED ON MONOETHYLENICALLY UNSATURATED DICARBONIC ACID ANHYDRIDES WITH AMINES OR ALCOHOLS FOR FAT AND FILL LEATHER OR FUR SKINS |
| DE4214011C1 (en) * | 1992-04-29 | 1993-11-04 | Muenzing Chemie Gmbh | COPOLYMERISATE |
| ES2090936T3 (en) * | 1992-06-09 | 1996-10-16 | Ciba Geigy Ag | PROCEDURE FOR THE FURTHER TREATMENT OF CURED LEATHER AND SKIN. |
| DE4223111A1 (en) * | 1992-07-14 | 1994-01-20 | Henkel Kgaa | New leather greasing agents and their use |
| DE4223110A1 (en) * | 1992-07-14 | 1994-01-20 | Henkel Kgaa | New leather greasing agents and their use (II) |
| GB9217547D0 (en) * | 1992-08-18 | 1992-09-30 | Allied Colloids Ltd | Leather treatment compositions |
| DE4236556A1 (en) * | 1992-10-29 | 1994-05-05 | Stockhausen Chem Fab Gmbh | Process for softening / greasing leather and fur |
| DE4242039A1 (en) * | 1992-12-12 | 1994-06-16 | Stockhausen Chem Fab Gmbh | Copolymers and their use for the treatment of leather |
| DE4400507A1 (en) * | 1994-01-12 | 1995-07-13 | Henkel Kgaa | Leather greasing agents |
| DE4402029A1 (en) * | 1994-01-25 | 1995-07-27 | Basf Ag | Aqueous solutions or dispersions of copolymers |
| DE4405205A1 (en) * | 1994-02-18 | 1995-08-24 | Henkel Kgaa | New leather greasing agents and their use |
| DE4416415A1 (en) * | 1994-05-10 | 1995-11-16 | Hoechst Ag | Copolymers based on ethylenically unsaturated dicarboxylic acid anhydrides, long-chain olefins and fluoroolefins |
| DE19508655A1 (en) | 1995-03-13 | 1996-09-19 | Basf Ag | Aqueous solutions or aqueous dispersions of copolymers of monoethylenically unsaturated dicarboxylic acids or their anhydrides and branched-chain oligomers or polymers |
| DE19516961A1 (en) * | 1995-05-12 | 1996-11-28 | Stockhausen Chem Fab Gmbh | Process for waterproofing leather at low pH values and leather produced therewith |
| DE19612986A1 (en) | 1996-04-01 | 1997-10-02 | Basf Ag | Use of copolymers based on ethylenically unsaturated dicarboxylic acids or dicarboxylic acid anhydrides, lower olefins and hydrophobic comonomers for retanning, greasing or hydrophobicizing leather and fur skins |
| DE19636494C2 (en) * | 1996-09-09 | 2000-11-16 | Stockhausen Chem Fab Gmbh | Low-monomer, amine-free polymers, processes for their preparation and their use in the production of low-fogging leather |
| US6753369B2 (en) | 2001-10-16 | 2004-06-22 | Buckman Laboratories International, Inc. | Leather waterproofing formulation and leather goods waterproofed therewith |
| EP1621640B1 (en) * | 2004-07-13 | 2006-10-04 | Zschimmer & Schwarz GmbH & Co KG Chemische Fabriken | Agent for the hydrophobic treatment of leather |
| DE102005029627A1 (en) * | 2005-06-23 | 2007-01-04 | Basf Ag | Process for the production of leather |
| JP2008012958A (en) * | 2006-07-03 | 2008-01-24 | Fujikura Parachute Co Ltd | Anti-g suit |
| CN102144024B (en) | 2008-07-07 | 2013-06-12 | 巴斯夫欧洲公司 | Enzyme composition comprising enzyme containing polymer particles |
| TWI531393B (en) | 2009-10-30 | 2016-05-01 | Ｆｌｎ消防用具諾伊魯平分部有限公司 | Composition suitable for production of foam extinguishants |
| DE102012201167A1 (en) | 2012-01-27 | 2013-08-01 | Evonik Industries Ag | Mixture composition containing amino-functional siloxanes, hydrophobic particles and high molecular weight silicones and its use for leather treatment |
| JP5941806B2 (en) * | 2012-09-27 | 2016-06-29 | 花王株式会社 | Method for producing polymer composition |
| JP6199125B2 (en) * | 2013-09-05 | 2017-09-20 | 花王株式会社 | Aqueous slurry |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2629748C2 (en) * | 1976-07-02 | 1979-06-07 | Zschimmer & Schwarz Chemische Fabriken, 5420 Lahnstein | Use of copolymers of monoolefins and maleic anhydride for filling and greasing leather and fur skins |
| ATE74620T1 (en) * | 1987-09-15 | 1992-04-15 | Basf Ag | FUELS FOR GASOLINE ENGINES. |
| DE3730885A1 (en) * | 1987-09-15 | 1989-03-23 | Basf Ag | Fuel for Otto engines (spark ignition engines) |
-
1989
- 1989-08-08 DE DE3926167A patent/DE3926167A1/en not_active Withdrawn
-
1990
- 1990-07-23 CA CA002021758A patent/CA2021758A1/en not_active Abandoned
- 1990-07-30 AT AT90114574T patent/ATE114727T1/en not_active IP Right Cessation
- 1990-07-30 ES ES90114574T patent/ES2064554T3/en not_active Expired - Lifetime
- 1990-07-30 EP EP90114574A patent/EP0412389B1/en not_active Revoked
- 1990-07-30 DE DE59007823T patent/DE59007823D1/en not_active Revoked
- 1990-08-06 PT PT94915A patent/PT94915B/en not_active IP Right Cessation
- 1990-08-06 NZ NZ234781A patent/NZ234781A/en unknown
- 1990-08-07 AU AU60227/90A patent/AU628205B2/en not_active Ceased
- 1990-08-07 JP JP2207708A patent/JPH0376800A/en active Pending
- 1990-08-08 KR KR1019900012136A patent/KR910004817A/en active IP Right Grant
Also Published As
| Publication number | Publication date |
|---|---|
| AU6022790A (en) | 1991-02-14 |
| DE59007823D1 (en) | 1995-01-12 |
| AU628205B2 (en) | 1992-09-10 |
| NZ234781A (en) | 1991-10-25 |
| EP0412389A1 (en) | 1991-02-13 |
| EP0412389B1 (en) | 1994-11-30 |
| ATE114727T1 (en) | 1994-12-15 |
| DE3926167A1 (en) | 1991-02-14 |
| PT94915B (en) | 1997-05-28 |
| JPH0376800A (en) | 1991-04-02 |
| KR910004817A (en) | 1991-03-29 |
| ES2064554T3 (en) | 1995-02-01 |
| PT94915A (en) | 1991-04-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2021758A1 (en) | Use of copolymers based on long-chain olefins and ethylenically unsaturated dicarboxylic anhydrides for rendering leathers and skins water-repellent | |
| US5124181A (en) | Copolymers based on long-chain unsaturated esters and ethylenically unsaturated carboxylic acids for making leather and furs water repellent | |
| US5286263A (en) | Use of copolymers based on long-chain alkyl vinyl ethers and ethylenically unsaturated dicarboxylic anhydrides for rendering leathers and skins water-repellent | |
| US5279613A (en) | Copolymers based on long-chain olefins and ethylenically unsaturated dicarboxylic anhydrides for rendering leathers and skins water-repellent | |
| EP0997539B1 (en) | Aqueous dispersion of copolymer for leather treatment | |
| US5534604A (en) | Copolymers based on ethylenically unsaturated dicarboxylic anhydrides, long-chain olefins and fluoroolefins | |
| WO1997037046A1 (en) | Use of copolymers based on ethylenically unsaturated dicarboxylic acids or dicarboxylic acid anhydrides, lower olefins and hydrophobic comonomers for after-tanning, stuffing or waterproofing leather and furs | |
| US5433752A (en) | Use of rection products of Homo- or copolymers based on monoethylenically unsaturated dicarboxylic anhydrides with amines or alcohols for fatliquoring and filling leather and fur skins | |
| US5820633A (en) | Method of treating leather with improved retaining agents | |
| US6336942B1 (en) | Processes of treating leather and skins employing polymer compositions | |
| US5330537A (en) | Leather treatment selected amphiphilic copolymer | |
| US5873908A (en) | Alkoxy group containing copolymers and their use in retanning leather | |
| AU718011B2 (en) | Aqueous polymer dispersion, process for preparing the same and its use in leather production | |
| US8822589B2 (en) | Method for the production of aqueous formulations, aqueous formulations, and the use thereof | |
| KR20050097973A (en) | Method for producing leather | |
| US20030180469A1 (en) | Composition and method for preparing leather |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |