A means to reduce the volatility of the ingredients of the skin
(57) Abstract:Usage: for retanning leather upholstery. The inventive skin is treated with the amphiphilic copolymer with an average mol. wt. 2500 to 50,000. The copolymer is obtained from more than 10 to less than 50 wt.% at least one hydrophilic monomer constituting the acrylic acid, methacrylic acid, taconova acid, fumaric acid, maleic acid, anhydrides of these acids; acid substituted (meth)acrylate, acid substituted (meth)acrylamide, basic substituted (meth)acrylate, basic substituted (meth)acrylamide or a mixture thereof, and from more than 50 to less than 90 wt.% at least one hydrophobic monomer constituting the alkyl(meth)acrylate, primary alkene, vinyl ether alkalicarbonate acid; alkylacrylate with the number of carbon atoms in the alkyl group of 4 to 12, alkylmethacrylamide with the number of carbon atoms in the alkyl group of 4 to 12, alkene -1 with the number of carbon atoms in the alkyl group of 4 to 12, vinyl ether alkalicarbonate acid with the number of carbon atoms in the alkyl group of 4 to 12, styrene, methylsterol, vinyl acetate, (meth)Acrylonitrile, n-alkyl(meth)acrylamide or a mixture of amphiphilic copolymer as a means to reduce leucaena as a means to reduce the volatility of the ingredients of the skin. Amphiphilic copolymer in the form of 20 - 60% aqueous solution is also used as a means to reduce the volatility of the ingredients of the skin. 2 C.p. f-crystals, 1 table. The invention relates to the use of fat liquor for retanning leather upholstery order to obtain acceptable strength characteristics and desired appearance and, most significantly, to ensure the lowest level of hazing that characterizes the reduction in the volatility of the ingredients of the skin.More specifically, the invention relates to the use of specially selected amphiphilic copolymer as a means to reduce the volatility of the ingredients of upholstery leather, used for finishing the vehicles.Further in the context of the invention, the term "fog" means the condensation evaporating volatile compounds coming from the interior finish of the vehicle, on the surface of the glass, especially on the windshield [see industrial standard DIN 75201 (April 1988)]
The term "(meth)acrylic" in the context of the invention means and acrylates, and methacrylates. For example, (meth)acrylate and (meth)acrylamide refers to the acrylates, methacrylates, acrylamides and methacrylamides sootvetstvenno, especially in the dark, in particular, when the driver operates the light of the oncoming traffic. The secondary effect is caused by particles of dust and dirt that enters the vehicle through the fan; these particles stick to the surface of the glass, causing further deterioration of sight.Requirements for physical properties and appearance that apply to a specific piece of leather, depend primarily on the nature of the end use of the leather. For example, one use case processing must first obtain the necessary strength; the external appearance of skin while you use plays a much smaller role.When using leather for the upholstery are important and durability, and appearance. When using leather for decoration of vehicles, such as automobiles and airplanes, tanned skin should reduce the volatility of its ingredients.Tanning of raw hides and skins with getting tanned leather includes a number of interrelated chemical and mechanical operations. Each of these operations affects the final properties of leather [see Leather Facts, New England Tanners (1972)] One of the important chemical operations for the dressing kublanow skin desired strength and softness. Fat solutions cuticles fiber skin so that after drying, the skin fibers are able to slide over each other. In addition to regulatory flexibility and softness of the skin, treatment of fatty solution strongly affects many aspects of your skin, as the limit of tensile strength and tensile strength. Processing fat solution also affects the nature of morenia skin when bending fibrous surface inside; the aim here is to obtain this skin, which after bending, no wrinkles or remains very little fine wrinkles.The main ingredients in the processing of body fluids by well-known methods are water-insoluble oils and fatty compounds, such as crude oils and sulphonated and sulfotyrosine oil. Typically, the weight fraction of oil fatty liquid is from 3 to 10% by weight of the skin.The way in which the oil is distributed in the skin, affects its properties, and on the subsequent closing operation. In order to obtain a uniform oil coating over a large surface fibers of the skin, it is usually necessary to dilute the oil with an organic solvent or preferably atomized oil in the aquatic environment, which however was installed, what are the main ingredients used for processing fat solutions, adversely affect such end-product characteristics, as the level of hazing.In Das Leder, 1988, edition of 9, Fat Liquors and "Fogging" -the influence of various raw materials and their processing methods, M. Kaussen, S. 161 165 (translation) indicates that the misting is all volatile compounds contained in the internal equipment, including compounds in the tissues, plastics and leather. The study of the mist produced by the skin, shows that a number of chemicals used in the standard processing operations of the skin, promotes the formation of fog; these include substances such as, for example, residual natural fats in the wet tanned leathers, phenolic fungicides, dyes, phthalates and additives mineral oil used as a dust additives; as well as solvents, emulsifiers and plasticizers used in the final stages.However, it was found that the most significant of all factors contributing to the blurring produced by the skin, are fats, and natural fats and fatty liquids, such as triglycerides and free fatty acids, which NR is AI degreasing reduce produced by the skin darken and suggested, that fat solutions used in the manufacture of upholstery leather for cars, should not, if possible, contain solvents or preferably be not very volatile compounds.On the basis of measurements of hazing in the publication Das Leder concludes that good results are achieved when using fat solutions based on sulfonated paraffins, sulphonated of chlorinated paraffin wax, sulfites wool fat and sulfites fish oil.In the publication Fogging Characteristics of Fat Liquors and Car Seat Leathers: Part I: Preliminary Studies, Samir das Gupta (11 may 1989) discusses the state of Affairs in the testing area of skin on the ball, especially in such methods as tests for reflection and gravimetric testing. In these tests was used a number of famous fat solutions. Attempts to establish a correlation between the content of volatile components in body fluids and the resulting levels of hazing has not led to success.In some respects the findings in the publication Das Gupta, on the basis of the assessments undertaken, particularly in relation sulphonated fish oil and sulphonated of chlorinated paraffin wax, opposite to the findings in Das Leder. As was skiscim testing; gravimetric testing is more accurate.Some car manufacturers have published their own methods for testing hazing and established their own requirements blurred. Some of these techniques are tested on reflection, such as Ford Motor Company, some include gravimetric testing, such as Daimler-Benz.The invention aims to overcome the problems of hazing associated with known methods of dressing the skin, in particular ensuring that reduce the volatility of the ingredients of the skin.The task according to the invention is achieved by the fact that as a means to reduce the volatility of the ingredients of the skin using amphiphilic copolymer with an average mol. wt. 2500 50000 formed from more than 10 to less than 50 wt. at least one hydrophilic monomer constituting the acrylic acid, methacrylic acid, taconova acid, fumaric acid, maleic acid, anhydrides of these acids; acid substituted (meth)acrylate, acid substituted (meth)acrylamide, basic substituted (meth)acrylate, basic substituted (meth)acrylamide or mixtures thereof, and from more than 50 to Malkin, vinyl ether alkalicarbonate acid, alkylacrylate with the number of carbon atoms in the alkyl group of 4 to 12, alkylmethacrylamide with the number of carbon atoms in the alkyl group of 4 to 12, alkene -1 with the number of carbon atoms from 4 to 12, vinyl ether alkalicarbonate acid with the number of carbon atoms in the alkyl group of 4 to 12, styrene, methylsterol, vinyl acetate, (meth)Acrylonitrile, n-alkyl(meth)acrylamide, olefin or a mixture.Specified amphiphilic copolymer described in the patent EP 0372746, CL C 14 C 9/00, 1990. Described in the patent amphiphilic copolymer is used to improve the aesthetic properties of the skin, gives it resistance, increases its durability and stretchability.According to the invention in a preferred embodiment, use of the proposed amphiphilic copolymer obtained by the emulsion polymerization in aqueous medium.Moreover, it is advisable to use amphiphilic copolymer as a means to reduce the volatility of the ingredients of the skin in the form of 20 to 60% aqueous solution.The proposed use of the copolymer allows you to get tanned skin with the required strength and softness, usually achievable using known fat solutions, and at the same time means is for the tanning of leather with doublelayer fat solution creating a low mist that does not contain organic solvent and containing a dispersion of selected amphiphilic copolymer formed by a large number of at least one hydrophobic monomer and a smaller amount of at least one copolymerizable with him hydrophilic monomer. The method of manufacture allows to obtain the skin with the necessary strength and softness and creates a low level of hazing. This tanned leather are particularly well suited for use as upholstery for vehicles.The amphiphilic copolymer is formed by more than 10 wt. but less than 50 wt. at least one hydrophilic monomer, and more than 50 wt. but less than 90 wt. at least one hydrophobic co monomer.More preferably the copolymer is formed by more than 15 wt. but less than about 45 wt. at least one hydrophilic monomer, and more than about 55 wt. but less than about 85 wt. at least one hydrophobic co monomer.Even more preferably the copolymer is formed by more than about 20 wt. but less than about 40 wt. at least one hydrophilic monomer, and more than about 60 wt. but less than about 80 wt. caeino polymerization in aqueous medium and in the form of a dispersion in water.Srednevekovaja mol. wt. amphiphilic copolymer is from about 2,500 to about 50,000.At least one hydrophilic comonomer used to obtain amphiphilic copolymer constitutes at least one monomer selected from water-soluble Ethylenediamine acidic or basic monomers, or mixtures thereof.Hydrophilic comonomer selected from the group consisting of acrylic acid, methacrylic acid, basis of itaconic acid, fumaric acid, maleic acid and anhydrides of these acids; acid substituted (meth)acrylates, acid substituted (meth)acrylamides and basic substituted (meth)acrylates and (meth)acrylamide, or mixtures thereof.Preferably the treated skin has a gravity value of less than 2 mg.At least one hydrophobic comonomer used to obtain amphiphilic copolymer is an alkyl(meth)acrylate, primary alkene, vinyl ether alkalicarbonate acid, alkylacrylate with the number of carbon atoms in the alkyl group of 4 to 12, alkylmethacrylamide with the number of carbon atoms in the alkyl group of 4 to 12, alkene -1 with the number of carbon atoms from 4 to 12, vinyl ether alkalicarbonate acid with the number of atoms in the d, the olefin or mixture of these compounds.Thus, the invention is directed to the use of dispersions of selected amphiphilic copolymers not containing organic solvents, for treatment of skin at the stage of processing the fat solution.Amphiphilic copolymers were selected for this purpose due to their ability to give the skin the necessary strength, softness and the desired appearance, and at the same time reduce the amount of mist produced processed fat solution leathers. It was found that the dispersion of amphiphilic copolymers according to the invention is preferably in the form of aqueous emulsions are "substantive", in other words, they remain in the treated skin and provide an exceptionally low level darken even in tough conditions.Selected amphiphilic copolymer must contain at least one hydrophobic and at least one hydrophilic group. The copolymer consists of more than 10 wt. but less than 50 wt. at least one hydrophilic monomer, and from more than 50 wt. but less than 90 wt. at least one hydrophobic co monomer.It is preferable that the copolymer consisted of more than 15 wt. but less than about 45 wt. as hydrophobic co monomer; even more preferably, the copolymer consisted of more than about 20 wt. but less than about 40 wt. at least one hydrophilic monomer, and from more than about 60 wt. but less than about 80 wt. at least one hydrophobic co monomer.The hydrophilic monomer used to obtain amphiphilic copolymer constitutes at least one monomer selected from the group consisting of water-soluble Ethylenediamine, preferably monomethylethanolamine acidic or basic monomers, and mixtures thereof.Examples of suitable hydrophilic monomers include acrylic acid, methacrylic acid, taconova acid, fumaric acid, maleic acid and anhydrides of such acids; acid substituted (meth)acrylates, such as, for example, Postretirement and sulfonethylmethane; acid substituted (meth)acrylamide, such as, for example, 2-acrylamide-2-methylpropanesulfonate; and osnovana substituted (meth)acrylates and (meth)acrylamide, such as, for example, aminosilane the methacrylates, including dimethylaminoethylmethacrylate, tert. -butylmethacrylate and dimethylaminoethylmethacrylate and similar.Preferred water-soluble hydrofil CLASS="ptx2">The choice of the nature and concentration of the hydrophilic monomer based on the desire to give the amphiphilic copolymer abilities well dispergirujutsja in the continuous phase, not containing organic solvents, for example in water, and to obtain amphiphilic copolymer with a high content of solid polymer particles and at the same time when such viscosity, which does not affect the treatment of the polymer and does not impair the ability of the polymer to penetrate the skin.Hydrophobic comonomer used to obtain amphiphilic copolymer constitutes at least one monomer selected from the group consisting of alkyl(meth)acrylates, primary alkenes, and vinyl esters alkylcarboxylic acids, and mixtures thereof. Suitable hydrophobic monomers include alkylacrylate with the number of carbon atoms in the alkyl group of 4 to 12, the alkyl methacrylates with the number of carbon atoms in the alkyl group of 4 to 12, alkenes -1 with the number of carbon atoms from 4 to 12, and vinyl esters alkylcarboxylic acids with the number of carbon atoms from 4 to 12. It was found that the preferred hydrophobic monomers that provide the best performance characteristics of amphiphilic copolymer, are alkyl(meth)acrylates with the number is relat.In combination with the predominant number (more than about 50 wt.) hydrophobic comonomers of at least one of the specified type, you can use smaller amounts of other Ethylenediamine copolymerizing monomers at concentrations equal to or less than 50 wt. the total concentration of hydrophobic co monomer. It was found that these incremental hydrophobic comonomers are diluents for other hydrophobic comonomers, without at the same time, the adverse effects on the properties of lipid solution containing amphiphilic copolymer.Examples of such copolymerizing hydrophobic comonomers diluents include styrene, methylstyrene, vinyl acetate, (meth)Acrylonitrile, n-alkyl(meth)acrylamide and olefins.Amphiphilic copolymer can be obtained by polymerization of hydrophilic and hydrophobic monomers using any known techniques of polymerization.It is established that it is preferable to carry out polymerization using standard methods of emulsion polymerization using water-soluble free radical initiator in a concentration of from about 0.1 wt. up to about 3 wt. of the total number of monomers. The polymerization preferably prostatitis circuit, for example, a mercaptan, for regulating molecular weight.Brednikova mol. wt. amphiphilic copolymer used according to the invention, can be from about 2,500 to about 100,000, preferably less than about 50,000.The polymerization can be conducted by mixing all the monomers at once or gradually adding the monomers to until polymerization is not essentially finished. Residual unreacted monomers can be introduced into the polymer by adding a new portion of the initiator of ways well known in the art. Polymerization allows the concentration of the amphiphilic polymer in the inorganic solvent in the range from about 20 to about 60 wt. solid polymer particles.The method of skin treatment includes skin exposure dispersion selected amphiphilic copolymer. The number used for skin treatment of the copolymer is from about 1 to about 20 wt. (based on solid polymer particles) from the weight of the skin, preferably from about 2 to about 15 wt. and most preferably from about 3 to about 12 wt.The choice of the relative amounts of hydrophobic and hydrophilic monomers used for Polemi, as will be demonstrated by examples.Used in the examples of amphiphilic copolymers were obtained according to the method described in example 1, varying the types and relative amounts of the monomers and the relative amount of carrier chain, and thus obtaining polymers with different molecular weight.Methods.The applicant evaluated amphiphilic copolymers according to the invention by comparing the appearance, strength, elasticity and darken skin treated with known fatty solutions that are considered "substaneasily", and skins, processed fat solutions according to the invention.The strength of the treated skin was determined according to the methods called elongation at "the cracking of the fibers and the elongation at the break of the ball". These techniques are commonly used in the art for evaluating the effectiveness of body fluids for lubrication and hardening of the skin. The test is designed to simulate the stretching of the skin on the pad in the manufacture of footwear, uses a device called Lastometer.In this test a strip of processed leather is clamped in the device, and then moving the clamp rastah the stand structure ("crack fibers") and at the moment, when the skin breaks (break of the ball"). The greater the elongation at cracking fibers and at break of the ball, the greater the strength of the skin.In addition to the assessment increase strength, achieved through the use of selected amphiphilic copolymers, the applicant also conducted a quantitative assessment of the softness of the skin. Softness is a measure of the flexibility and elasticity of the skin; the higher the softness, the greater the flexibility and elasticity of the skin. The softness of the treated skin samples was measured using a compression tester Hunter-Spring, modified according Stubbings and E. Senfelder JALCA, vol 58, No. 1, January 1963, and established as the minimum criterion is soft, about equal 3810 μm (150 miles).In addition to assessing the strength and softness of the treated skin, the applicant also carried out a qualitative evaluation of the appearance of the treated skin. This was done by the characteristics of the treated skin samples using rating scales, in accordance with which the skin was defined as soft, firm or hard.Characteristics hazing doublelayer fat solutions based on amphiphilic copolymers was determined by gravimetric test method. Specific test method that b is, rhodesi testing, were dried for 7 days in a desiccator with phosphorus pentoxide. Each gravimetric measurement was performed twice. Presents the results are expressed in mass measured (condensed) fog; and the smaller this value, the better the result. According to the gravimetric test acceptable low levels of hazing are less than 2 mg.Preparation of skins.Compare results for selected amphiphilic doublelayer fat solutions and some of the famous fat solutions, referred to as "substaneasily" fat solutions. Skin, cooked according to the following method (reference method) were used to evaluate two well-known industrial labotatories fat solutions: sulfochlorinated oil and sulfonylamino fish oil. For processing leathers selected doubleValue solutions based on amphiphilic copolymers of the present invention was used Methodology A.The method is applicable, however, to other types of hides and skins of animals (such as pigskin, sheepskin and so on), for example, leathers and skins mineral (chromium, aluminum is mean weight, equal to the weight of raw material in the drum).Unless otherwise noted, all skin were made from pieces of cow skins chrome tanning weight from 85,05 g (3 oz) (thickness 1,19 mm) up to 99.2 g (3.5 oz) (thickness 1,389 mm).Control methods.1) Raw material for 30 min washed with water at 40oC with the open door of a drum.2) In a dryer at 40oC was added 100% liquid (liquid refers to water: 100% fluid means adding water in a quantity equal to the weight of raw materials), and then were added 2% sodium acetate and 0.25% sodium bicarbonate. The resulting mixture was rolled in the drum (mixed) within 120 minutes3) Then the liquid from the drum decanted and raw materials for 15 min at 50oC was rinsed with water at the door of the drum.4) In the drum at 46 54oC was added 100% liquid.5) Standard doublebase agent (6,0% Leukotan 970 when the solids content of 32% which corresponds to 1.9% of active Leukotan) were diluted with an equal weight amount of water and added to the contents of the drum through the journal (open reel). The resulting mixture was rolled in the drum 30 min (Leukotan is a trademark of Rohm and Haas Company).6) Then add 1% formic acid is ivali of the drum liquid. Added to the drum 200% liquid at 50oC, then add the fat solution based sulfochlorinated oil (65% active component) dispersed in 20% of water at 50oC, and then spinning the resulting mixture for 60 minutes8) Then was added with 1.0% formic acid for fixation fat solution and spun raw materials in the dryer for 15 min, then poured the liquid out of it.9) Raw material for 15 min at a temperature of 35oC was washed with the open door.10) Then the raw materials were placed on a wooden frame and left in this position until the morning.11) Then the raw material is hung out to dry, whereupon they were kondicionirovanie within 1 to 7 days at a constant temperature equal to 22.2oC (72oF) in the room, and a relative humidity of 60% and then stretched on the hare (subjected to mechanical abating).Methodology A.1) Raw material for 30 min washed with water at a temperature of 40oC with the open door.2) In a dryer at 40oC was added 100% liquid, and then added 2% sodium acetate and 0.25% sodium bicarbonate. The resulting mixture was spun in the dryer for 4 hours3) Then the liquid from the drum poured in echegaray 100% liquid with vigorous stirring was added or sodium hydroxide (in the case of a copolymer with acidic hydrophilic copolymer), or formic acid (in the case of a copolymer with a basic hydrophilic monomer) in a quantity sufficient to neutralize about 75% of a polymeric acid or a polymeric base, respectively. Then dispersed thus 100% liquid copolymer was added to the raw material in the tanning drum, and the resulting mixture was spun in the dryer for 60 minutes at 50oC. Loading amphiphilic copolymer was 6 wt. the weight of raw materials (unless otherwise specified).5) Then add 1% formic acid, previously diluted to 10% solution (in the case of acidic hydrophilic co monomer), or 1% sodium bicarbonate (in the case of a conventional hydrophilic co monomer), and spinning raw materials in the dryer for 15 min at 50oC. Stage was repeated to bring the pH of the liquid in the drum to 4.0 or less.6) was Poured from the drum liquid and when the door was washed raw materials for 15 min at a temperature of 35oC.7) Then the raw material is put for the night on a wooden frame.8) After that, the raw materials were hung to dry and then kondicionirovanie within 1 to 7 days at a constant temperature of 22.2oC (72oF) and a relative humidity of 60% and then stretched h-ethylhexyl acrylate /30 wt. methacrylic acid.Polymerization was performed in a nitrogen atmosphere in chetyrehkolkoy round bottom flask with a volume of 1 l, equipped with a paddle stirrer of Teflon in the Central throat, thermometer and reflux condenser. Into the flask was loaded 185 g of deionized water, 4 g of lauryl sodium, 1 drop of sulfuric acid and 0.3 g of 1% aqueous solution of ferrous sulfate iron.Then the mixture was heated to 60oC. the Monomers (140 g 2-ethylhexyl acrylate and 60g methacrylic acid) together with 10 g of n-dodecylmercaptan (carrier chain) was emulsiable with 95 g of deionized water and 4 g laurylsulphate sodium, and simultaneously with the initiators in the reaction flask over 3 hours, maintaining the temperature of the reaction mixture at 60oC, was injected 0.6 g of ammonium persulfate dissolved in 22 g of water and 0.6 g of sodium bisulfite dissolved in 22 g of water.After adding the residual monomer exceeded in the polymer using "bullet" add another 0.1 g of redox and free radical initiators. Then the emulsion polymer was cooled and pH adjusted by the addition of 20.4 g of a 13% aqueous solution of sodium hydroxide. The final product consisted of 37.8 wt. solid compound by using a copolymer of polyacrylic acid as a standard, was 8200, and Brednikova molecular weight of 6600.Example 2. The evaluation of the properties of the treated skin.According to the described methods was assessed properties will not be processed fat solution skin samples ("raw"), processed amphiphilic copolymers according to the invention skin samples, and processed famous comparative substaneasily fat solutions skin samples ("..").The results are shown in the table.In this table, all gravimetric tests blurred (DIN 75201, modified as described) were repeated twice, are the results of both tests; to denote the monomers used to produce synthetic copolymers for body fluids, used the following abbreviations:
AK acrylic acid;
MAC methacrylic acid;
EGO hexyl acrylate;
BA butyl acrylate;
CAME citratesildenafil.In addition, used the following abbreviations: ARV elongation at cracking fibers; UR elongation; h hard, tons of hard, soft.The results show is on the required strength and softness, but the low level of hazing. 1. The use of amphiphilic copolymer with an average mol.m. 2500 50000 formed from more than 10 to less than 50 wt. at least one hydrophilic monomer constituting the acrylic acid, methacrylic, taconova, fumaric, maleic, anhydride of these acids; acid substituted (meth)acrylate, acid substituted (meth)acrylamide, basic substituted (meth)acrylate, basic substituted (meth)acrylamide or a mixture thereof, and from more than 50 wt. to less than 90 wt. at least one hydrophobic monomer constituting the alkyl(meth)acrylate, primary alkene, vinyl ether alkalicarbonate acid, alkylacrylate with the number of carbon atoms in the alkyl group of 4 to 12, alkylmethacrylamide with the number of carbon atoms in the alkyl group of 4 to 12, alkene-1 with the number of carbon atoms of 4 to 12, vinyl ether alkalicarbonate acid with the number of carbon atoms in the alkyl group of 4 to 12, styrene, methylsterol, vinyl acetate, (meth)Acrylonitrile, n-alkyl(meth)acrylamide or a mixture thereof, as a means to reduce the volatility of the ingredients of the skin.2. The use of amphiphilic copolymer under item 1, obtained by the emulsion polymerization in aqueous medium, as a means to reduce volatility phrases is a means to reduce the volatility of the ingredients of the skin.
FIELD: tannery industry, in particular method for syntan (synthetic tanning material) production.
SUBSTANCE: claimed method includes diphenolepropane sulgation and condensation with formaldehyde followed by acidifying with sulfuric acid. Formed product is dispersed in lignosulfates containing 0.5-1.5 % of aluminum sulfate as calculated to aluminum oxide.
EFFECT: syntans with stable content of tanned materials: environmentally friendly and economical process.
FIELD: chemistry of polymers, leather industry, chemical technology.
SUBSTANCE: invention relates to a method for preparing polymeric products that are used in processes for dressing leather or fur, in treatment and disinfection of natural and sewage waters. Method for preparing polymeric products involves the hydroxymethylation reaction of polyhexamethylene guanidine chloride with formaldehyde and arylation reaction of prepared product with aromatic compound comprising o-amino- or o-hydroxy-groups. The hydroxymethylation reaction is carried out in the presence of acetic acid or formic acid up to formation of trimethylol derivative of polyhexamethylene guanidine chloride. In some cases the arylation product is subjected for complex formation with transient metal salt or azo-coupling reaction with diazonium salt taken among group including sulfanilic acid, naphthionic acid, j-naphthyls, p-nitroaniline, 2,6-dichloro-4-nitroaniline. Invention provides simplifying, accelerating and enhancing the effectiveness of process in dressing leathers with derivatives of polyhexamethylene guanidine showing tanning effect, staining properties, flocculating capacity and high antibacterial activity.
EFFECT: improved preparing method.
3 cl, 1 tbl, 9 ex
SUBSTANCE: invention relates to graft polymers based on polysaccharides and polypeptides. Graft polymer based on polysaccharides and polypeptides or respective derivatives thereof are obtained by free-radical polymerisation of A) a monomer selected from following, or a mixture of following monomers: (a) from 20 to 100 wt% acrylic acid or methacrylic acid, or mixture thereof, or salts thereof with an alkali metal, alkali-earth metal or ammonium, (b) from 0 to 80 wt% other monoethylenically unsaturated monomers, which can be copolymerised with monomer (a) and (c) from 0 to 5 wt% monomers containing per molecule at least 2 ethylenically unsaturated unconjugated double bonds in presence of B1) polysaccharides subjected to oxidative, hydrolytic or enzymatic decomposition, oxidised polysaccharides subjected to hydrolytic decomposition or subjected to enzymatic decomposition, or chemically modified decomposed products, chemically modified mono-, oligo-or polysaccharides, or mixtures of said compounds and B2) polypeptides subjected to hydrolytic or enzymatic decomposition and optionally chemically modified polypeptides, or mixtures of said compounds, with weight ratio A:(B1+B2) ranging from 60:40 to 1:99 and B1:B2 from 97:3 to 3:97. Also disclosed is a method of producing graft polymers, method of tanning leather, and tanned leather.
EFFECT: wider range of polymers for various types of tanning.
7 cl, 18 ex
FIELD: leather industry.
SUBSTANCE: semifinished product is degreased, neutralized, dyed, and lubricated. Dyeing is performed in two washing-interrupted steps with anionic black dye consumed in amount 0.5-0.6% of the weight of semifinished product in each dyeing step. Lubrication is followed by retannage with chrome tanner in amount 0.6-1.0% of the weight of semifinished product (calculated for chromium oxide) and treatment with 0.8-1.0% of spindle oil.
EFFECT: achieved deep black color and high performance characteristics.
1 tbl, 5 ex
FIELD: tannery or furry production.
SUBSTANCE: the invention is pertaining to the field of tannery or furry production and may be used for a piece by piece treatment of a tanning, furry semi-finished product with emulsions of "water in oil" type. The device for impregnation of sheets contains a mounted on the frame bath with a working compound, in which a corrugated roller is dipped, and also a feeding and auxiliary conveyers and a smoothing roller, a supporting means with a resilient counterbody, an actuator, a tool for removal of a finished semi-product, a device for creation of a hydrodynamic wedge and a pinch roller for engagement of the ribbed roller with the feeding conveyor. The problem of the presented invention is - development of the device simple in its servicing with a high reliability allowing to realize the process of impregnation more efficiently with a possibility of its installation in an automatic production line.
EFFECT: the invention presents a device simple in its servicing, having a high reliability, more efficient realization of the process of impregnation, a possibility of its usage in an automatic production line.
FIELD: tannery industry.
SUBSTANCE: claimed method includes treatment of chrome-tanned semi-finished product with antiseptic such as polymineral obtained from natural non-metal fossils (minerol), which is used in amount of 5-10 mass % based on semi-finished product. Minerol is also used as filler being introduced in retanning step with chrome compounds in amount of 5-10 mass % based on semi-finished product.
EFFECT: effective biological leather conservation after chrome tanning.
3 cl, 1 tbl
FIELD: chemical technology.
SUBSTANCE: invention relates to greasing and emulsifying substances used in fur, leather and other branches of industry. Invention describes a method for deep sulfonation of oxidized vegetable oils, fats and their mixtures, and oxidized mixtures with the nominal viscosity value in the range 33-75 by viscosimeter VZ-4 at 20°C in their treatment with sodium sulfite. The process is carried out in system consisting of oxidized component or mixture of oxidized components, sodium sulfite, water and soap additives, carboxylic acid, phenol and copper (II) salt as a catalyst in bead mill of vertical type at temperature of environment up to practically complete ceasing or quantitative consumption of sodium sulfite and charge of the latter is calculated by the following formula: mNA2SO3 = 0.006 x mOX x (I.N.)OX wherein mOX and (I.N.)OX mean mass and iodine number of oxidized component or mixture of oxidized components, respectively. The mass ratio of oxidized component and water varies in the range from 1:4 to 1:2.5. Dosing additives with respect to oxidized component are following: soap, 2%; carboxylic acid, 4%; phenol, 2.5%. Oxidized flax, sunflower, soybean and cotton oils, oxidized fish oil and mixtures of vegetable oils with fish oil or pig fat are subjected for sulfonation reaction with air in regimen of intensive bubble bubbling at 105 ± 5°. Soaps in indicated system are represented by sodium stearate and sodium oleate and by reaction mixtures of practically quantitative alkaline hydrolysis of fats and vegetable oils also. Benzoic, oxalic, malonic and citric acids are used as acid, and sulfate, acetate and other water-soluble salts of copper (II) are sued as a catalyst dosed in the amount (2-7.5) x 10-4 mole/kg of the parent charge. The sulfonation reaction degree is 33-40%.
EFFECT: improved preparing method.
5 cl, 1 tbl, 16 ex
FIELD: tanning industry.
SUBSTANCE: process is conducted in vertical mill to which soot, induline, kerosene and diesel fuel are introduced. Then components are mixed and slow heating the apparatus and its content is started after which mixing is switched off and slow heating of mill content is continued. Upon expiration of said time, acids or their compositions, white spirit and fatty additive are introduced and chemical mass-exchange process is performed at spontaneously fixed temperature due to thermal effects of this process and natural cooling at the beginning and at the end, as well as due to forced cooling at intermediate stage characterized by high rates of temperature at maximum of 140-150°C. At the moment when forced cooling is discontinued, 0.5-1.5 h before discontinuation of mixing and beginning of withdrawal at temperature of 80-115°C, 43-52-% solution of aluminum salts and C10-C20 of carboxylic acids is introduced into product being prepared.
EFFECT: facilitated procedure; increased amount of product.
1 tbl, 15 ex
FIELD: leather industry.
SUBSTANCE: preparation of composition is conducted on vertical-type bead mill. Induline, kerosene, and diesel fuel are consecutively charged into mill before stirring mechanism is energized, after which apparatus and contents thereof are slowly heated. Stirring is then stopped for 1 h while slow heating of mill contents is continued. When specified time expires, carboxylic acid or acid mixture, white spirit, fat additive, and aluminum oxide or hydroxide are added. Mechanic stirring is then switched on and contents of the bead mill are ground and the process is carried out at spontaneously fixed temperature caused by heat effects of the processes and natural cooling. When temperature is lowered to 85-120°C, desired product is discharged.
EFFECT: simplified process and increased product discharge degree.
1 tbl, 19 ex