CN101519702A - Polyhydroxyalkylphosphine-organosilicone tanning agent, preparation and application thereof in fur tanning - Google Patents
Polyhydroxyalkylphosphine-organosilicone tanning agent, preparation and application thereof in fur tanning Download PDFInfo
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- CN101519702A CN101519702A CN200810007505A CN200810007505A CN101519702A CN 101519702 A CN101519702 A CN 101519702A CN 200810007505 A CN200810007505 A CN 200810007505A CN 200810007505 A CN200810007505 A CN 200810007505A CN 101519702 A CN101519702 A CN 101519702A
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- 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
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/08—Chemical tanning by organic agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/395—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing phosphorus
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Abstract
The invention relates to a polyhydroxyalkylphosphine-organosilicone tanning agent, preparation and application thereof in fur tanning. The tanning agent consists of polyhydroxyalkylphosphine, organosilicone with molecular weight being 1 to 200000, a surface active agent, a stabilizing agent and purified water. The preparation method of the tanning agent comprises the steps of adding the organosilicone in a kettle, stirring and heating up to 40 to120 DEG C, adding the surface active agent and continuing stirring for 20 to 90 minutes, and controlling the temperature within the range of 40 to 120 DEG C; adding the purified water, stirring and cooling to 40 to 90 DEG C; adding the polyhydroxyalkylphosphine, continuing stirring for 60 to 120 minutes and adjusting pH to 4 to 6; adding the stabilizing agent and stirring for 30 to 60 minutes; cooling to 20 to 50 DEG C; and taking the agent out of the kettle. The tanning agent is applied to fur tanning and is low in destructive power to fleece of the fur, the tanned leather has good resistance to dry/washing and is not detanning; the tanning agent self has low toxicity without potential safety hazard, does not accumulate in organism, and has no carcinogenicity, teratogenicity or transgenation; and the applied tanning technology has low temperature, short time and low energy consumption, and is forehanded and environment-friendly.
Description
Technical field
The present invention relates to a kind of multi-hydroxy alkyl phosphine-organosilicone tanning agent, relate to a kind of novel environment friendly leather retanning agent that is adapted to the leather tanning technology that less energy-consumption, low gross loss hinder and preparation method thereof and the application in fur tanning specifically.
Technical background
At present, leather tanning extensively adopts following several process for tanning: 1) metal tanning agent tanning is the best representative with chrome tanning matter.Chrome tanning system promptly utilizes trivalent chromium and rawhide collagen protein network and effect to reach leather tanning.Other metal tanning agent tan leather principles with chrome tanning system, but effect is relatively poor, aluminum tanning system for example, zirconium tanning system.2) vegetable extract tanning: the leather physical properties of tanning is very special, mainly is adsorbed between the leather fiber by intermolecular forces.Main now application special dimension or the auxiliary tanning of application.3) aldehyde tannage: the formaldehyde tanning is a process for tanning early, because the environmental protection factor, use has been under an embargo.The glutaraldehyde tanning effect is an ideal method comparatively in the chrome-free tanning, mainly is by reaching the tanning purpose with amino combination of albumen.4) oxazolidine tannings: be a kind of tanning effect bating method without chrome preferably, mechanism is similar to aldehyde tannage.5) phosphine tanning: by reaching the tanning effect with amino combination of albumen.
Patent CN1071956 has comprised hydroxyalkyl phosphine and derivative thereof in sheepskin pretan with to the crosslinked application of casein finishing agent.CN1278304 has comprised the technology of using the methylol phosphine or using the polymkeric substance tan leather of methylol phosphine and aminocompound or amine.CN1345368 has comprised the compound that utilizes methylol phosphine and chromium and has carried out the leather tanning technology.CN1357053 has comprised the methylol phosphine and buffer mixture is applied to tanning.PCT/EP2000/00084 comprised the methylol phosphine in conjunction with small additions of chromium and an amount of nonionic/or cats product be applied to tanning, so that than using separately the methylol phosphine to compare to improve yield of leather and shrinkage temperature, and compare reduction to environmental influence with the tanning of independent application chrome tanning agent.
Comprised application methylol phosphine and zirconium tanning agent is produced pink wet pelt leather by the USpatent7252687 of inventions such as Chandrabose.Domestic Li Ya etc. have studied the tanning mechanism (" Chinese leather " 2005/19 phase) of Tetrakis hydroxymethyl phosphonium chloride (THPC).Guo Wenyu etc. have studied the synthetic and application (" Chinese leather " 2006/09 phase) of tetra methylol phosphine-aluminum tanning agent.Guo Wenyu etc. have discussed exploitation and application prospect (" Chinese leather " 2004/03 phase thereof of a kind of phosphonium salt tanning agent.Li Ya etc. have studied tris(hydroxymethyl)phosphine (THP) salt and have combined the research of tanning (" fine chemistry industry " 2006 08 phases with the Dyhard RU 100 original position.
The single application polyhydroxy alkyl of above-mentioned prior art phosphine compound or derivatives thereof contacts with hair matter, in tannery hair has all been caused damage in various degree.Add organosilicon and close the damage that can significantly reduce hair, but can reduce contacting of polyhydroxy alkyl phosphine compound and mao matter with hair knot, mao dyeing behavior be lowered, cause and dye difficulty or dying phenomenon.How when not influencing polyhydroxy alkyl phosphine compound and hair matter and contact, can guarantee the dyeing behavior of hair again, and reduce the damage of hair as much as possible, become tanning industry technical problem suddenly to be solved.
Summary of the invention
The object of the present invention is to provide a kind of in tannery, there is the organosilicon of certain molecular weight and special property to combine with hair matter equably, after tanning finishes, have special tensio-active agent to be removed again, thereby but even dyeing also guarantee multi-hydroxy alkyl phosphine-organosilicone tanning agent that hair matter is intact and preparation method thereof and the application in fur tanning.
The object of the present invention is achieved like this: a kind of multi-hydroxy alkyl phosphine-organosilicone tanning agent, it is made up of organosilicon 10-100 part, tensio-active agent 2-10 part, stablizer 1-10 part and pure water 10-300 part of polyhydroxy alkyl phosphine 500-1500 part, molecular weight ranges 1-20 ten thousand.
Wherein, polyhydroxy alkyl phosphine general formula is: (HO-R) nP, and wherein, R is the positive alkyl of C1-20 chain length, n=1-4; Can be tetrahydroxy alkyl phosphonium salt, trihydroxy-alkylphosphines and dihydroxyl alkylphosphines and monohydroxy alkylphosphines.Preferred Tetrakis hydroxymethyl phosphonium chloride, tris(hydroxymethyl)phosphine.
Wherein, the organosilicon of molecular weight ranges 1-20 ten thousand is silicone oil, containing hydrogen silicone oil, amino or hydroxyl or methyl-silicone oil or containing hydrogen silicone oil, and contained amino or amount of hydroxyl groups are less than 10%.
Wherein, tensio-active agent is one or several in dodecyl alcohol polyoxyethylene (3) ether (AEO-3), dodecyl alcohol polyoxyethylene (9) ether (AEO-9), dodecyl alcohol polyoxyethylene (10) ether (AEO-10), dodecyl alcohol polyoxyethylene (15) ether (AEO-15), dodecyl alcohol polyoxyethylene (20) ether (AEO-20), Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, imidazoline amophoteric surface active agent, alkyl quaternary ammonium salts, alkyl tert ammonium salt, alkylamine polyoxyethylene (15) ether or the alkyl alcohol polyethenoxy ether sodium sulfate.
Wherein, stablizer is white sugar, glycerine, trolamine, diethanolamine, Monoethanolamine MEA BASF or Stearyl alcohol.
Wherein, a kind of preparation method of multi-hydroxy alkyl phosphine-organosilicone tanning agent comprises 10-100 part organosilicon is added in the reactor, stirs and be warming up to 40-120 ℃, adds 2-10 part tensio-active agent and continues to stir 20-90min, controlled temperature 40-120 ℃; Add pure water 10-300 part, stir, and be cooled to 40-90 ℃; Add 500-1500 part polyhydroxy alkyl phosphine, continue to stir 60-120min, adjust pH4-6; Add 1-10 part stablizer, stir 30-60min; Be cooled to 20-50 ℃; Go out still.
Wherein, the application of multi-hydroxy alkyl phosphine-organosilicone tanning agent in fur tanning comprises that technology is as follows:
1. pre-treatment before the pickling: with 20-40 ℃ of washing, add nonionogenic tenside 1 grams per liter, formic acid 0.2 grams per liter is handled 30-90min;
2. pickling: salt 60-70 grams per liter, temperature 10-40 ℃, water liquor ratio 1-60 kilogram/open adds formic acid 5 grams per liters, sulfuric acid 0.5 grams per liter, sanitas 0.1 grams per liter, and pH2.5-3 soaks 18-48hr;
3. tanning: salt 60 grams per liters, temperature 18-40 ℃, water liquor ratio 1-60 kilogram/open, add formic acid, sulfuric acid and sodium formiate, make pH3.0-5.0, add multi-hydroxy alkyl phosphine-organosilicone tanning agent 2-8 grams per liter, tanning 1-18hr, gradation in 1-8 hour adds soda ash 4-6 grams per liter, adds to continue to stir 1-8hr;
4. check: shrinkage temperature then can go out skin greater than 75 ℃ during pH5-7;
5. fixing: water liquor ratio 1-60 kilogram/open, water temperature 20-50 ℃, hydrogen peroxide 1-30 grams per liter, glycerine 0-10 grams per liter, the Biquest0.1-0.5 grams per liter rotates 0.5-24hr;
6. reduction: water liquor ratio 1-60 kilogram/open, temperature 45-65 ℃, float a mao powder 2-8 grams per liter, riquest 0-1 grams per liter rotates 1-8hr;
7. washing: water liquor ratio 1-60 kilogram/open, temperature 20-55 ℃, tensio-active agent 0-3 grams per liter, Briquest 0-1 grams per liter, acetic acid 0-1 grams per liter changes 10-30min, toggling, dry-cleaning, arrangement, dyeing;
8. degreasing: water liquor ratio 1-60 kilogram/open, temperature 30-50 ℃, grease-removing agent 0.5-3 grams per liter, soda ash 0-2 grams per liter soaks 30-60min;
9. dye hair: water liquor ratio 1-60 kilogram/open, temperature 55-70 ℃, levelling agent 0.2-2 grams per liter, ammoniacal liquor 0-2 grams per liter changes 10min, adds dyestuff 0.1-3 grams per liter, changes 20-60min, adds formic acid 0.2-1 grams per liter, and pH3-4 changes 30min, 2-5 time altogether;
10. pickling: water liquor ratio 1-60 kilogram/open, normal temperature, formic acid 0.2-1 grams per liter is washed 20min, 2-4 time altogether, gets final product.
The present invention compared with prior art, its is used polyhydroxy alkyl phosphine and prepares jointly with organosilicon mixture, has selected special tensio-active agent simultaneously, and is low to the destructive force of fur fleece, mao damage few; The fur gloss of institute's tanning, the shrinkage temperature height, color is vivid; Leather sweat proof, ageing-resistant has good anti-doing/washing property, and tempering does not guarantee the permanent usability of leather, tear strength and tensile strength height; The water-absorbent of using product tanning wiping leather of the present invention is big, and wiping effect is good.Can produce pure white leather and high temperature resistant xanthochromia and light xanthochromia; Tan leather health, finished product do not contain toxic heavy metals such as chromium, and formaldehyde content is lower than 20PPM, and do not contain other aldehyde such as glutaraldehyde, and have good flame-retarding, but finished product rubbish natural degradation or burning disposal; In the process for tanning, do not use harmful sterilant such as pentachlorophenol; Process hides system fur coat technology whole process, water-based degreasing is fully thoroughly removed organic solvent human body is endangered; It is low to use the process for tanning temperature, and the time is short, and it is low to consume energy, economical environment-protective; Can improve the absorption of dyestuff, fixing, reduce the use 1/3 of dyestuff, dyeing waste colourity reduces; The hypotoxicity of this tanning agent own, in using concentration, pH scope, no potential safety hazard; To the hydrocoles hypotoxicity, itself can natural degradation, degradation half life 26-28 days; Tanning agent can not accumulated in vivo, non-carcinogenesis, teratogenecity and transgenation; Production technique is simple, is easy to control, detects, and can ensure the product stable and consistent.
Embodiment
Further specify the present invention below in conjunction with embodiment
Embodiment 1: a kind of composition of multi-hydroxy alkyl phosphine-organosilicone tanning agent
500 kilograms of Tetrakis hydroxymethyl phosphonium chloride,
100 kilograms of the amido silicon oils of molecular weight ranges 1-20 ten thousand,
2 kilograms in dodecyl alcohol polyoxyethylene (3) ether (AEO-3),
10 kilograms of white sugar and
10 kilograms of pure water.
Embodiment 2: a kind of composition of multi-hydroxy alkyl phosphine-organosilicone tanning agent
1500 kilograms of tris(hydroxymethyl)phosphines,
10 kilograms of the hydroxyl hydrogen silicone oils of molecular weight ranges 1-20 ten thousand,
10 kilograms in dodecyl alcohol polyoxyethylene (9) ether (AEO-9),
1 kilogram of glycerine and
300 kilograms of pure water.
Embodiment 3: a kind of composition of multi-hydroxy alkyl phosphine-organosilicone tanning agent
1000 kilograms of Tetrakis hydroxymethyl phosphonium chloride,
55 kilograms of the methyl-silicone oils of molecular weight ranges 1-20 ten thousand,
6 kilograms in dodecyl alcohol polyoxyethylene (10) ether (AEO-10),
5.5 kilograms of trolamines and
155 kilograms of pure water.
Embodiment 4: a kind of composition of multi-hydroxy alkyl phosphine-organosilicone tanning agent
750 kilograms of tris(hydroxymethyl)phosphines,
30 kilograms of the amino containing hydrogen silicone oils of molecular weight ranges 1-20 ten thousand,
8 kilograms in dodecyl alcohol polyoxyethylene (15) ether (AEO-15),
3 kilograms of diethanolamine and
230 kilograms of pure water.
Embodiment 5: a kind of composition of multi-hydroxy alkyl phosphine-organosilicone tanning agent
1300 kilograms of Tetrakis hydroxymethyl phosphonium chloride,
80 kilograms of the hydroxy silicon oils of molecular weight ranges 1-20 ten thousand,
4 kilograms in dodecyl alcohol polyoxyethylene (20) ether (AEO-20),
8 kilograms of Monoethanolamine MEA BASFs and
80 kilograms of pure water.
Embodiment 6: a kind of composition of multi-hydroxy alkyl phosphine-organosilicone tanning agent
1000 kilograms of tris(hydroxymethyl)phosphines,
10 kilograms of the Methyl Hydrogen Polysiloxane Fluids of molecular weight ranges 1-20 ten thousand,
10 kilograms of Sodium dodecylbenzene sulfonatees,
5.5 kilograms of Stearyl alcohols and
10 kilograms of pure water.
Embodiment 7: a kind of composition of multi-hydroxy alkyl phosphine-organosilicone tanning agent
1000 kilograms of Tetrakis hydroxymethyl phosphonium chloride,
100 kilograms of the amido silicon oils of molecular weight ranges 1-20 ten thousand,
2 kilograms of sodium lauryl sulphate,
5.5 kilograms of white sugar and
300 kilograms of pure water.
Embodiment 8: a kind of composition of multi-hydroxy alkyl phosphine-organosilicone tanning agent
1500 kilograms of tris(hydroxymethyl)phosphines,
55 kilograms of the hydroxyl hydrogen silicone oils of molecular weight ranges 1-20 ten thousand,
2 kilograms of imidazoline amophoteric surface active agents,
10 kilograms of glycerine and
155 kilograms of pure water.
Embodiment 9: a kind of composition of multi-hydroxy alkyl phosphine-organosilicone tanning agent
500 kilograms of Tetrakis hydroxymethyl phosphonium chloride,
55 kilograms of the methyl-silicone oils of molecular weight ranges 1-20 ten thousand,
10 kilograms of alkyl quaternary ammonium saltss,
1 kilogram of trolamine and
155 kilograms of pure water.
Embodiment 10: a kind of composition of multi-hydroxy alkyl phosphine-organosilicone tanning agent
1500 kilograms of tris(hydroxymethyl)phosphines,
10 kilograms of the containing hydrogen silicone oils of molecular weight ranges 1-20 ten thousand,
6 kilograms of alkyl tert ammonium salts,
10 kilograms of diethanolamine and
10 kilograms of pure water.
Embodiment 11: a kind of composition of multi-hydroxy alkyl phosphine-organosilicone tanning agent
500 kilograms of Tetrakis hydroxymethyl phosphonium chloride,
100 kilograms of the silicone oil of molecular weight ranges 1-20 ten thousand,
6 kilograms in alkylamine polyoxyethylene (15) ether,
1 kilogram of Monoethanolamine MEA BASF and
300 kilograms of pure water.
Embodiment 12: a kind of composition of multi-hydroxy alkyl phosphine-organosilicone tanning agent
1400 kilograms of tris(hydroxymethyl)phosphines,
20 kilograms of the containing hydrogen silicone oils of molecular weight ranges 1-20 ten thousand,
8 kilograms of alkyl alcohol polyethenoxy ether sodium sulfates,
2 kilograms of Stearyl alcohols and
250 kilograms of pure water.
Embodiment 13: a kind of composition of multi-hydroxy alkyl phosphine-organosilicone tanning agent
600 kilograms of Tetrakis hydroxymethyl phosphonium chloride,
90 kilograms of the silicone oil of molecular weight ranges 1-20 ten thousand,
2 kilograms in dodecyl alcohol polyoxyethylene (3) ether (AEO-3),
1 kilogram in dodecyl alcohol polyoxyethylene (9) ether (AEO-9),
1 kilogram of Sodium dodecylbenzene sulfonate,
8 kilograms of white sugar and
30 kilograms of pure water.
Embodiment 14: a kind of preparation of multi-hydroxy alkyl phosphine-organosilicone tanning agent
According to the embodiment 1 described composition component of measuring, organosilicon is added in the reactor, stir and be warming up to 40 ℃, add tensio-active agent and continue to stir 90min, 40 ℃ of controlled temperature.Add pure water, stir, and be cooled to 40 ℃.Add the polyhydroxy alkyl phosphine, continue to stir 120min, adjust pH6.Add stablizer, stir 60min.Be cooled to 20 ℃.Going out still gets final product.
Embodiment 15: a kind of preparation of multi-hydroxy alkyl phosphine-organosilicone tanning agent
According to the embodiment 2 described composition component of measuring, organosilicon is added in the reactor, stir and be warming up to 120 ℃, add tensio-active agent and continue to stir 20min, 120 ℃ of controlled temperature.Add pure water, stir, and be cooled to 90 ℃.Add the polyhydroxy alkyl phosphine, continue to stir 60min, adjust pH4.Add stablizer, stir 30min.Be cooled to 50 ℃.Going out still gets final product.
Embodiment 16: a kind of preparation of multi-hydroxy alkyl phosphine-organosilicone tanning agent
According to the embodiment 3 described composition component of measuring, organosilicon is added in the reactor, stir and be warming up to 80 ℃, add tensio-active agent and continue to stir 55min, 80 ℃ of controlled temperature.Add pure water, stir, and be cooled to 65 ℃.Add the polyhydroxy alkyl phosphine, continue to stir 90min, adjust pH5.Add stablizer, stir 45min.Be cooled to 35 ℃.Going out still gets final product.
Embodiment 17: a kind of preparation of multi-hydroxy alkyl phosphine-organosilicone tanning agent
According to the embodiment 13 described composition component of measuring, organosilicon is added in the reactor, stir and be warming up to 90 ℃, add combinations-of surfactants and continue to stir 40min, 70 ℃ of controlled temperature.Add pure water, stir, and be cooled to 60 ℃.Add the polyhydroxy alkyl phosphine, continue to stir 100min, adjust pH5.Add stablizer, stir 40min.Be cooled to 40 ℃.Going out still gets final product.
Embodiment 18: the application of a kind of multi-hydroxy alkyl phosphine-organosilicone tanning agent in fur tanning technology comprises following technology:
1. pre-treatment before the pickling: with 20 ℃ of washings, add nonionogenic tenside 1 grams per liter, formic acid 0.2 grams per liter is handled 90min;
2. pickling: salt 60 grams per liters, 40 ℃ of temperature, 1 kilogram/of water liquor ratio adds formic acid 5 grams per liters, sulfuric acid 0.5 grams per liter, sanitas 0.1 grams per liter, and pH2.5-3 soaks 48hr;
3. tanning: salt 60 grams per liters, 18 ℃ of temperature, 60 kilograms/of water liquor ratios, add formic acid, sulfuric acid and sodium formiate, make pH3.0-5.0, add embodiment 14 described multi-hydroxy alkyl phosphine-organosilicone tanning agent 2 grams per liters, tanning 18hr, gradation in 1 hour adds soda ash 6 grams per liters, adds to continue to stir 1hr;
4. check: shrinkage temperature then can go out skin greater than 75 ℃ during pH5-7;
5. fixing: 60 kilograms/of water liquor ratios, 20 ℃ of water temperatures, hydrogen peroxide 30 grams per liters, Biquest 0.5 grams per liter rotates 0.5hr;
6. reduction: 60 kilograms/of water liquor ratios, 45 ℃ of temperature are floated mao powder 8 grams per liters, rotate 8hr;
7. washing: 1 kilogram/of water liquor ratio, 55 ℃ of temperature, Briquest 1 grams per liter changes 30min, toggling, dry-cleaning, arrangement, dyeing;
8. degreasing: 1 kilogram/of water liquor ratio, 50 ℃ of temperature, grease-removing agent 0.5 grams per liter, soda ash 2 grams per liters soak 30min;
9. dye hair: 60 kilograms/of water liquor ratios, 55 ℃ of temperature, levelling agent 2 grams per liters change 10min, add dyestuff 3 grams per liters, change 20min, add formic acid 1 grams per liter, and pH3-4 changes 30min, totally 2 times;
10. pickling: 60 kilograms/of water liquor ratios, normal temperature, formic acid 0.2 grams per liter is washed 20min, totally 4 times, gets final product.
Embodiment 19: the application of a kind of multi-hydroxy alkyl phosphine-organosilicone tanning agent in fur tanning technology comprises following technology:
1. pre-treatment before the pickling: with 40 ℃ of washings, add nonionogenic tenside 1 grams per liter, formic acid 0.2 grams per liter is handled 30min;
2. pickling: salt 70 grams per liters, 10 ℃ of temperature, 60 kilograms/of water liquor ratios add formic acid 5 grams per liters, sulfuric acid 0.5 grams per liter, sanitas 0.1 grams per liter, and pH2.5-3 soaks 18hr;
3. tanning: salt 60 grams per liters, 40 ℃ of temperature, 1 kilogram/of water liquor ratio, add formic acid, sulfuric acid and sodium formiate, make pH3.0-5.0, add embodiment 15 described multi-hydroxy alkyl phosphine-organosilicone tanning agent 8 grams per liters, tanning 1hr, gradation in 8 hours adds soda ash 4 grams per liters, adds to continue to stir 8hr;
4. check: shrinkage temperature then can go out skin greater than 75 ℃ during pH5-7;
5. fixing: 1 kilogram/of water liquor ratio, 50 ℃ of water temperatures, hydrogen peroxide 1 grams per liter, glycerine 10 grams per liters, Biquest 0.1 grams per liter rotates 24hr;
6. reduction: 1 kilogram/of water liquor ratio, 65 ℃ of temperature are floated mao powder 2 grams per liters, and the riquest1 grams per liter rotates 1hr;
7. washing: 60 kilograms/of water liquor ratios, 20 ℃ of temperature, tensio-active agent 3 grams per liters, acetic acid 1 grams per liter changes 10min, toggling, dry-cleaning, arrangement, dyeing;
8. degreasing: 60 kilograms/of water liquor ratios, 30 ℃ of temperature, grease-removing agent 3 grams per liters soak 60min;
9. dye hair: 1 kilogram/of water liquor ratio, 70 ℃ of temperature, levelling agent 0.2 grams per liter, ammoniacal liquor 2 grams per liters change 10min, add dyestuff 0.1 grams per liter, change 60min, add formic acid 0.2 grams per liter, and pH3-4 changes 30min, totally 5 times;
10. pickling: 1 kilogram/of water liquor ratio, normal temperature, formic acid 1 grams per liter is washed 20min, totally 2 times, gets final product.
Embodiment 20: the application of a kind of multi-hydroxy alkyl phosphine-organosilicone tanning agent in fur tanning technology comprises following technology:
1. pre-treatment before the pickling: with 30 ℃ of washings, add nonionogenic tenside 1 grams per liter, formic acid 0.2 grams per liter is handled 60min;
2. pickling: salt 65 grams per liters, 25 ℃ of temperature, 30 kilograms/of water liquor ratios add formic acid 5 grams per liters, sulfuric acid 0.5 grams per liter, sanitas 0.1 grams per liter, and pH2.5-3 soaks 33hr;
3. tanning: salt 60 grams per liters, 29 ℃ of temperature, 30 kilograms/of water liquor ratios, add formic acid, sulfuric acid and sodium formiate, make pH3.0-5.0, add embodiment 16 described multi-hydroxy alkyl phosphine-organosilicone tanning agent 5 grams per liters, tanning 9hr, gradation in 4 hours adds soda ash 5 grams per liters, adds to continue to stir 5hr;
4. check: shrinkage temperature then can go out skin greater than 75 ℃ during pH5-7;
5. fixing: 30 kilograms/of water liquor ratios, 35 ℃ of water temperatures, hydrogen peroxide 15 grams per liters, glycerine 50 grams per liters, Biquest 0.3 grams per liter rotates 12hr;
6. reduction: 30 kilograms/of water liquor ratios, 55 ℃ of temperature are floated mao powder 5 grams per liters, and the riquest0.5 grams per liter rotates 4hr;
7. washing: 30 kilograms/of water liquor ratios, 37 ℃ of temperature, tensio-active agent 1.5 grams per liters, Briquest 0.5 grams per liter, acetic acid 0.5 grams per liter changes 20min, toggling, dry-cleaning, arrangement, dyeing;
8. degreasing: 30 kilograms/of water liquor ratios, 40 ℃ of temperature, grease-removing agent 2 grams per liters, soda ash 1 grams per liter soaks 45min;
9. dye hair: 30 kilograms/of water liquor ratios, 60 ℃ of temperature, levelling agent 1 grams per liter, ammoniacal liquor 1 grams per liter changes 10min, adds dyestuff 1.5 grams per liters, changes 40min, adds formic acid 0.6 grams per liter, and pH3-4 changes 30min, totally 4 times;
10. pickling: 30 kilograms/of water liquor ratios, normal temperature, formic acid 0.6 grams per liter is washed 20min, totally 3 times, gets final product.
Embodiment 21: the application of a kind of multi-hydroxy alkyl phosphine-organosilicone tanning agent in fur tanning technology comprises following technology:
1. pre-treatment before the pickling: with 35 ℃ of washings, add nonionogenic tenside 1 grams per liter, formic acid 0.2 grams per liter is handled 50min;
2. pickling: salt 66 grams per liters, 30 ℃ of temperature, 40 kilograms/of water liquor ratios add formic acid 5 grams per liters, sulfuric acid 0.5 grams per liter, sanitas 0.1 grams per liter, and pH2.5-3 soaks 30hr;
3. tanning: salt 60 grams per liters, 25 ℃ of temperature, 25 kilograms/of water liquor ratios, add formic acid, sulfuric acid and sodium formiate, make pH3.0-5.0, add embodiment 17 described multi-hydroxy alkyl phosphine-organosilicone tanning agent 5 grams per liters, tanning 10hr, gradation in 5 hours adds soda ash 5 grams per liters, adds to continue to stir 4hr;
4. check: shrinkage temperature then can go out skin greater than 75 ℃ during pH5-7;
5. fixing: 35 kilograms/of water liquor ratios, 30 ℃ of water temperatures, hydrogen peroxide 16 grams per liters, glycerine 4 grams per liters, Biquest 0.4 grams per liter rotates 13hr;
6. reduction: 31 kilograms/of water liquor ratios, 55 ℃ of temperature are floated mao powder 5 grams per liters, and riquest 0.6 grams per liter rotates 5hr;
7. washing: 25 kilograms/of water liquor ratios, 35 ℃ of temperature, tensio-active agent 2 grams per liters, Briquest 0.4 grams per liter, acetic acid 0.6 grams per liter changes 20min, toggling, dry-cleaning, arrangement, dyeing;
8. degreasing: 34 kilograms/of water liquor ratios, 40 ℃ of temperature, grease-removing agent 1.8 grams per liters, soda ash 1 grams per liter soaks 45min;
9. dye hair: 30 kilograms/of water liquor ratios, 60 ℃ of temperature, levelling agent 1.1 grams per liters, ammoniacal liquor 1 grams per liter changes 10min, adds dyestuff 1.6 grams per liters, changes 40min, adds formic acid 0.6 grams per liter, and pH3-4 changes 30min, totally 3 times;
10. pickling: 32 kilograms/of water liquor ratios, normal temperature, formic acid 0.5 grams per liter is washed 20min, totally 3 times, gets final product.
Embodiment 22: a kind of gross loss of multi-hydroxy alkyl phosphine-organosilicone tanning agent is hindered test
A kind of multi-hydroxy alkyl phosphine of patent CN1071956 product A and embodiment 1-organosilicone tanning agent W produces sheep shorn velvet leather according to same technical process, measures the woolen alkali dissolution.
------oxidation---reduction---drying is got dry back fur antimere wool and pickling raw material skin and is detected alkali dissolution in tanning in technical process: pickled skin.
Test method: get a sheepskin, the place makes circular mark at the ridge line, and hair is taken off dry, and measures caustic solubility.Simultaneously, be divided into two (by circular label diameter) according to the ridge line, two splits are done A and W comparative study according to above-mentioned technical process respectively.
Trial sheet: pickled skin is the big production product of factory, is slunks.Derive from Jiaozhuo, Henan Long Feng leather and fur existing company is arranged.
Equipment: paddle-tumble
Tanning: liquor ratio=50 kg of water/open skin temperature 20 to spend
Salt 60 grams per liters
Formic acid 0.5 grams per liter
Briquest 301-50A 1 grams per liter rotates 30 fens pH4.5
A or B 6 grams per liters rotated 240 fens
Soda ash 4 grams per liters change 240 minutes (gradation adds, 30 minutes at interval)
Washing: normal temperature washing 10 minutes
Drying-sampling-detection wool caustic solubility, measuring method detects according to the ISO method.
The sampling spot of hair is near the circular mark, according to hair sampling on the hide symmetric position.
Measurement result: the woolen alkali solubility is respectively on the wool leather that application product A and tanning are finished: 25% and 17%.The alkali solubility of pickling raw material skin is 15%.
Test-results:
Utilize W tanning woolfell, the woolen damage rate is: (17-15)/and 15=13.33%
Utilize A tanning woolfell, the woolen damage rate is: (25-15)/and 15=66.67%
This test confirms that product W of the present invention can reduce the wool damage rate and reach 53.33%.
Embodiment 23: a kind of dyeing behavior test of multi-hydroxy alkyl phosphine-organosilicone tanning agent
Applicating example: the production New Zealand sheepskin integumentary pattern (long-woolskin) that becomes mildewed.
The raw material skin: New Zealand's salt marsh slunks, integumentary pattern is complete, no knife wound cavity, dermatotome does not have severe contamination.
Tanning equipment: stainless steel or glass reinforced plastic paddle-tumble
Liquid coefficient: 50 a kg of water/skin
Production technique: embodiment 18 described technologies
Result: even dyeing.
Embodiment 24: toxicology test
Acute toxicity: breathe and suck LC50 (rat) 5.55mg/litre/4h.
Per os LD50 (rat) 575mg/kg
Skin LD50 (rat)〉2000mg/kg
Subacute and chronic toxicity:
Pungency :-nose; Larynx and respiratory system can not cause serious stimulation
-skin adopts " semi-occlusive " individual layer to paste the stimulation phenomenon that the method meter caused minimum degree in 4 hours on rabbit skin
Chronic toxicity/carinogenicity: to mouse (two property) F344/N and B6C3F1 with 5 or 10mgTHPS feed and do not find carinogenicity in 2 years.
Mutagenicity: bacillary mutagenesis (Ames)-feminine gender
This product can not cause that DNA's is unordered synthetic.
The mortality analysis main to the mouse live body is negative.
Toxicity regeneration/development: after mouse and rabbit research,, do not have the toxicity orthogenesis existing under the remarkable former toxic situation.
The mouse test when dosage is the 15mg/kg body weight, is not observed toxicity Influence and Development level.
The rabbit test when dosage is the 18mg/kg body weight, is not observed toxicity Influence and Development level.
Embodiment 24: ecological test
Ecological total sight the: enter the waters as product, can not cause severe bad influence to environment.
Mobile: this product is water-soluble.
Persistence/degradation property: under excess oxygen, the product readily biodegradable also precipitates in water system.Reached 60% degraded in 28 days.
Under anaerobic, product readily biodegradable and in water system, precipitating.Reached 60% degraded in 30 days.
Eco-toxicity: to rainbow trout test 96 hours, dosage 119mg/litre, LC50;
To bluegill sunfish test 96 hours, dosage 93mg/litre, LC50;
To Daphnia magna test 48 hours, dosage 19.4mg/litre, EC50;
To wild duck test, dosage 113mg/KG, LD50;
To brown shrimp test 96 hours, dosage 340mg/litre, LC50;
To plaice test childhood 96 hours, dosage 86mg/litre, LC50;
To Corophium Volutator test 10 hours, dosage 2174mg/KG (dried weight of precipitate), LC50.
Claims (9)
1, a kind of multi-hydroxy alkyl phosphine-organosilicone tanning agent, it is made up of organosilicon 10-100 part, tensio-active agent 2-10 part, stablizer 1-10 part and pure water 10-300 part of polyhydroxy alkyl phosphine 500-1500 part, molecular weight ranges 1-20 ten thousand.
2, the described a kind of multi-hydroxy alkyl phosphine-organosilicone tanning agent of claim 1 is characterized in that polyhydroxy alkyl phosphine general formula is: (HO-R) nP, wherein, R is the positive alkyl of C1-20 chain length, n=1-4.
3, the described a kind of multi-hydroxy alkyl phosphine-organosilicone tanning agent of claim 1 is characterized in that the polyhydroxy alkyl phosphine is tetrahydroxy alkyl phosphonium salt, trihydroxy-alkylphosphines and dihydroxyl alkylphosphines and monohydroxy alkylphosphines.Preferred Tetrakis hydroxymethyl phosphonium chloride, tris(hydroxymethyl)phosphine.
4, the described a kind of multi-hydroxy alkyl phosphine-organosilicone tanning agent of claim 1 is characterized in that the polyhydroxy alkyl phosphine is Tetrakis hydroxymethyl phosphonium chloride, tris(hydroxymethyl)phosphine.
5, the described a kind of multi-hydroxy alkyl phosphine-organosilicone tanning agent of claim 1, the organosilicon that it is characterized in that molecular weight ranges 1-20 ten thousand is silicone oil, containing hydrogen silicone oil, amino or hydroxyl or methyl-silicone oil or containing hydrogen silicone oil, contained amino or amount of hydroxyl groups are less than 10%.
6, the described a kind of multi-hydroxy alkyl phosphine-organosilicone tanning agent of claim 1 is characterized in that tensio-active agent is one or several in dodecyl alcohol polyoxyethylene 3 ethers, dodecyl alcohol polyoxyethylene 9 ethers, dodecyl alcohol polyoxyethylene 10 ethers, dodecyl alcohol polyoxyethylene 15 ethers, dodecyl alcohol polyoxyethylene 20 ethers, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, imidazoline amophoteric surface active agent, alkyl quaternary ammonium salts, alkyl tert ammonium salt, alkylamine polyoxyethylene 15 ethers or the alkyl alcohol polyethenoxy ether sodium sulfate.
7, the described a kind of multi-hydroxy alkyl phosphine-organosilicone tanning agent of claim 1 is characterized in that stablizer is white sugar, glycerine, trolamine, diethanolamine, Monoethanolamine MEA BASF or Stearyl alcohol.
8, the preparation of the described a kind of multi-hydroxy alkyl phosphine-organosilicone tanning agent of claim 1 comprises 10-100 part organosilicon is added in the reactor, stirs and be warming up to 40-120 ℃, adds 2-10 part tensio-active agent and continues to stir 20-90min, controlled temperature 40-120 ℃; Add pure water 10-300 part, stir, and be cooled to 40-90 ℃; Add 500-1500 part polyhydroxy alkyl phosphine, continue to stir 60-120min, adjust pH4-6; Add 1-10 part stablizer, stir 30-60min; Be cooled to 20-50 ℃; Go out still.
9, the application of the described multi-hydroxy alkyl phosphine-organosilicone tanning agent of claim 1 in fur tanning comprises that technology is as follows:
1) pre-treatment before the pickling: with 20-40 ℃ of washing, add nonionogenic tenside 1 grams per liter, formic acid 0.2 grams per liter is handled 30-90min;
2) pickling: salt 60-70 grams per liter, temperature 10-40 ℃, water liquor ratio 1-60 kilogram/open adds formic acid 5 grams per liters, sulfuric acid 0.5 grams per liter, sanitas 0.1 grams per liter, and pH2.5-3 soaks 18-48hr;
3) tanning: salt 60 grams per liters, temperature 18-40 ℃, water liquor ratio 1-60 kilogram/open, add formic acid, sulfuric acid and sodium formiate, make pH3.0-5.0, add multi-hydroxy alkyl phosphine-organosilicone tanning agent 2-8 grams per liter, tanning 1-18hr, gradation in 1-8 hour adds soda ash 4-6 grams per liter, adds to continue to stir 1-8hr;
4) check: shrinkage temperature then can go out skin greater than 75 ℃ during pH5-7;
5) fixing: water liquor ratio 1-60 kilogram/open, water temperature 20-50 ℃, hydrogen peroxide 1-30 grams per liter, glycerine 0-10 grams per liter, the Biquest0.1-0.5 grams per liter rotates 0.5-24hr;
6) reduction: water liquor ratio 1-60 kilogram/open, temperature 45-65 ℃, float a mao powder 2-8 grams per liter, the riquest0-1 grams per liter rotates 1-8hr;
7) washing: water liquor ratio 1-60 kilogram/open, temperature 20-55 ℃, tensio-active agent 0-3 grams per liter, the Briquest0-1 grams per liter, acetic acid 0-1 grams per liter changes 10-30min, toggling, dry-cleaning, arrangement, dyeing;
8) degreasing: water liquor ratio 1-60 kilogram/open, temperature 30-50 ℃, grease-removing agent 0.5-3 grams per liter, soda ash 0-2 grams per liter soaks 30-60min;
9) dye hair: water liquor ratio 1-60 kilogram/open, temperature 55-70 ℃, levelling agent 0.2-2 grams per liter, ammoniacal liquor 0-2 grams per liter changes 10min, adds dyestuff 0.1-3 grams per liter, changes 20-60min, adds formic acid 0.2-1 grams per liter, and pH3-4 changes 30min, 2-5 time altogether;
10) pickling: water liquor ratio 1-60 kilogram/open, normal temperature, formic acid 0.2-1 grams per liter is washed 20min, 2-4 time altogether, gets final product.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810007505A CN101519702A (en) | 2008-02-26 | 2008-02-26 | Polyhydroxyalkylphosphine-organosilicone tanning agent, preparation and application thereof in fur tanning |
| NZ587314A NZ587314A (en) | 2008-02-26 | 2009-02-24 | Poly hydroxyl alkyl phosphine-organic silicon tanning agent, its preparation and application in fur tanning |
| CN200980107010.2A CN101965412B (en) | 2008-02-26 | 2009-02-24 | Poly hydroxyl alkyl phosphine-organic silicon tanning agent, its preparation and application in fur tanning |
| PCT/CN2009/000193 WO2009105963A1 (en) | 2008-02-26 | 2009-02-24 | Poly hydroxyl alkyl phosphine-organic silicon tanning agent, its preparation and application in fur tanning |
| AU2009218972A AU2009218972B2 (en) | 2008-02-26 | 2009-02-24 | Poly hydroxyl alkyl phosphine-organic silicon tanning agent, its preparation and application in fur tanning |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810007505A CN101519702A (en) | 2008-02-26 | 2008-02-26 | Polyhydroxyalkylphosphine-organosilicone tanning agent, preparation and application thereof in fur tanning |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101519702A true CN101519702A (en) | 2009-09-02 |
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Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200810007505A Pending CN101519702A (en) | 2008-02-26 | 2008-02-26 | Polyhydroxyalkylphosphine-organosilicone tanning agent, preparation and application thereof in fur tanning |
| CN200980107010.2A Expired - Fee Related CN101965412B (en) | 2008-02-26 | 2009-02-24 | Poly hydroxyl alkyl phosphine-organic silicon tanning agent, its preparation and application in fur tanning |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200980107010.2A Expired - Fee Related CN101965412B (en) | 2008-02-26 | 2009-02-24 | Poly hydroxyl alkyl phosphine-organic silicon tanning agent, its preparation and application in fur tanning |
Country Status (4)
| Country | Link |
|---|---|
| CN (2) | CN101519702A (en) |
| AU (1) | AU2009218972B2 (en) |
| NZ (1) | NZ587314A (en) |
| WO (1) | WO2009105963A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102127606A (en) * | 2010-01-19 | 2011-07-20 | 深圳市绿微康生物工程有限公司 | Method for retanning leather by using bioenzyme |
| CN102453776A (en) * | 2010-10-26 | 2012-05-16 | 北京泛博科技有限责任公司 | Tanning agent and preparation method thereof |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103710474B (en) * | 2012-09-29 | 2016-09-21 | 焦作隆丰皮草企业有限公司 | A kind of process for tanning of sheep shearing |
| CN107345261B (en) * | 2017-08-07 | 2019-06-25 | 陕西科技大学 | Eight carboxyl silsesquioxane tanning agent of water solubility and its method based on the preparation of mercaptan-alkene clicking chemistry method |
| CN115197361B (en) * | 2022-07-26 | 2023-08-15 | 四川亭江新材料股份有限公司 | Acrylic ester polymer tanning agent and preparation method thereof |
| CN115404570A (en) * | 2022-09-22 | 2022-11-29 | 桐乡市恒隆化工有限公司 | FDY oil agent for superfine denier fibers and preparation method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS605640B2 (en) * | 1977-04-27 | 1985-02-13 | 東洋エアゾ−ル工業株式会社 | Leather polishing agent |
| JPS5923760B2 (en) * | 1981-11-09 | 1984-06-04 | 日華化学工業株式会社 | Leather manufacturing method |
| GB9120652D0 (en) * | 1991-09-27 | 1991-11-06 | Albright & Wilson | Use of phosphonium compounds in the preparation of leather |
| GB0013611D0 (en) * | 2000-06-06 | 2000-07-26 | Rhodia Cons Spec Ltd | Tanning leather |
| US7252687B2 (en) * | 2004-12-23 | 2007-08-07 | Council Of Scientific And Industrial Research | Process for making wet-pink leather |
| CN100500870C (en) * | 2006-11-09 | 2009-06-17 | 宁波工程学院 | Preparation method of tetra hydroxy methyl phosphonium salt chromium-less tanning agent |
-
2008
- 2008-02-26 CN CN200810007505A patent/CN101519702A/en active Pending
-
2009
- 2009-02-24 CN CN200980107010.2A patent/CN101965412B/en not_active Expired - Fee Related
- 2009-02-24 AU AU2009218972A patent/AU2009218972B2/en not_active Ceased
- 2009-02-24 WO PCT/CN2009/000193 patent/WO2009105963A1/en active Application Filing
- 2009-02-24 NZ NZ587314A patent/NZ587314A/en not_active IP Right Cessation
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102127606A (en) * | 2010-01-19 | 2011-07-20 | 深圳市绿微康生物工程有限公司 | Method for retanning leather by using bioenzyme |
| CN102453776A (en) * | 2010-10-26 | 2012-05-16 | 北京泛博科技有限责任公司 | Tanning agent and preparation method thereof |
| CN102453776B (en) * | 2010-10-26 | 2014-04-30 | 北京泛博科技有限责任公司 | Tanning agent and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2009218972B2 (en) | 2013-06-13 |
| WO2009105963A1 (en) | 2009-09-03 |
| CN101965412A (en) | 2011-02-02 |
| AU2009218972A1 (en) | 2009-09-03 |
| NZ587314A (en) | 2012-09-28 |
| CN101965412B (en) | 2013-09-25 |
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Application publication date: 20090902 |