WO 2009/105963 PCT/CN2009/000193 POLY HYDROXYL ALKYL PHOSPHI1E-ORGANIC SILICON TANNING AGENT, ITS PREPARATION AND APPLICATION IN FUR TANNING 5 Technical Field This invention relates to a poly hydroxyl alkyl phosphine-organic silicon tanning agent, its preparation and application in fur tanning. Specifically, it relates to a new environmental protection leather tanning agent that adapts to the leather tanning technology of low energy consumption and low fur damage, its preparation, and its 10 application in fur tanning. Background At present, several tanning methods as follows are widely used in leather tanning: 1) Tanning with metal tanning agent: Chromium tanning matter is the most superior 15 representative. Chromium tanning uses the ligation effect of trivalent chromium and raw hide collagen protein to achieve leather tanning. The principle of leather tanning with other metal tanning agents is the same as that of chromium tanning, but their effect is poorer. Examples are aluminum tanning, zirconium tanning etc. 2) Plant tannin extract tanning: The physical property of the tanned leather is extremely special. It 20 mainly relies on the intra-molecular force to be absorbed into the leather fibers. Now it is mainly used in special fields and applied in auxiliary tanning. 3) Aldehyde tanning: Methyl aldehyde tanning is used in earlier times. Due to the factor of environmental protection, it has been prohibited from use. The effect of pentane dialdehyde tanning is more ideal. It mainly combines with protein amino to achieve the objective of tanning. 25 4) Oxazolidine tanning: It is a non-chromium tanning method with better tanning effect. Its mechanism is similar to that of aldehyde tanning. 5) Phosphine tanning: It achieves the tanning effect through combining with protein amino. Patent CN10711956 covers the application of hydroxyl alkyl phosphine and its derivatives in sheep skin pre-tanning and the cross-linking of casein finishing agent.
WO 2009/105963 PCT/CN2009/000193 CN1278304 covers the leather tanning technology that applies hydroxyl methyl phosphine or applies the polymer of hydroxyl methyl phosphine and amino compound or ammonia. CN1345368 covers the leather tanning technology that utilizes the compound of hydroxyl methyl phosphine and chromium. CN1357053 covers the 5 application of the mixture of hydroxyl methyl phosphine and buffer agent in tanning. The US patent 7252687 (Chandrabose et al.) covers the utilization of hydroxyl methyl phosphine and zirconium to produce pink wet leather. In China, Li Ya et al. have studied the tanning mechanism of tetra hydroxymethyl phosphorus chloride (THPC) ("China Leather" Issue 2005/19). Guo Wenyu et al. have studied the synthesis 10 and application of tetra hydroxyl methyl phosphine-aluminum tanning agent ("China Leather" Issue 2006/09). Guo Wenyu et al. have discussed the development and application prospect of a type of phosphine salt tanning agent ("China Leather" Issue 2004/03). Li Ya et al. has studied the in situ combined tanning of tri hydroxymethyl phosphine (TlP) and dicyandiamide ("Fine Chemical Industry" Year 2006 Issue 08). 15 The existing technology described above applies the contact between poly hydroxyl alkyl phosphine compound or its derivatives and the fur material. In the process of tanning, different degree of damage is caused to the fur. The addition of organic silicon that combines with the fur can greatly decrease the damage of fur. However, it decreases the contact between poly hydroxyl alkyl phosphine compound 20 and the fur material. The dying function of the fur is decreased, causing dying difficulty or dye chemical effect. In the tanning industry, how to guarantee the dying function of the fur and minimize the damage to the fur without affecting the contact between poly hydroxyl alkyl phosphine and the fur material has become a technical problem that awaits solution. 25 Invention Details The objective of this invention is to provide a kind of organic silicon with certain molecular mass and special property that evenly combines with the fur material in the process of tanning. After tanning is finished, the organic silicon is removed by a special 2 WO 2009/105963 PCT/CN2009/000193 surface active agent. In this way, the dying can be even, and it can be guaranteed that the fur material is intact. The objective of this invention is met by a poly hydroxyl alkyl phosphine-organic silicon tanning agent that comprises 500-1,500 parts of poly hydroxyl alkyl phosphine, 5 10-100 parts of organic silicon of molecular mass range 10,000-200,000, 2-10 parts of surface active agent, 1-10 parts of stabilizer and 10-300 parts of pure water. The tanning agent according to the instant invention is suitable for the treatment of any kind of skin animals and is more particularly suitable for the treatment of woolskins also called woolfells. 10 In particular, the general formula of poly hydroxyl alkyl phosphine is (HO-R)n P, wherein R is ortho-alkyl whose chain length is in C1 -20 having 1 to 20 carbon atoms, and n = 1-4. The poly hydroxyl alkyl phosphine can be selected from the group comprising tetra hydroxyl methyl phosphine salt, tri hydroxyl alkyl phosphine and di hydroxyl alkyl phosphine and mono hydroxyl alkyl phosphine. Tetra hydroxyl methyl 15 phosphine salt and tri hydroxyl alkyl phosphine are preferred. In particular, the organic silicon of molecular mass range 10,000-200,000 is silicon oil, hydrogen-containing silicon oil, amino, hydroxyl or methyl silicon oil or hydrogen-containing silicon oil that contains less than 10% of amino or hydroxyl quantity. 20 In particular, the surface active agent is one or several of 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), dodecyl benzene sodium sulfonate, dodecyl sodium sulfate, imidazoline 25 double-property surface active agent, alkyl quaternary ammonium salt, alkyl tertiary ammonium salt, alkyl amine polyoxyethylene (15) ether or alkyl alcohol polyoxyethylene ether sodium sulfate. In particular, the stabilizer is white sugar, glycerol, triethanolamine, diethanolamine, monoethanolanine or octadecyl alcohol. 3 WO 2009/105963 PCT/CN2009/000193 The instant invention also relates to a method of preparation of the poly hydroxyl alkyl phosphine-organic silicon tanning agent of the present invention, comprising the steps of: adding 10-100 parts of organic silicon into a reactor vessel, 5 stirring and heating up to 40-120'C, adding 2-10 parts of surface active agent, continuing stirring for 20-90min, controlling temperature at 40-120 C; adding 10-300 parts of pure water, stirring, and heating up to 40-90'C; 10 adding 500-1,500 parts of poly hydroxyl alkyl phosphine, continuing stirring for 60-120min, adjusting pH4-6; adding 1-10 parts of stabilizer, stirring for 30-60min; cooling down to 20-50'C; and recovering the poly hydroxyl alkyl phosphine-organic silicon tanning agent from 15 vessel. In particular, the preparation method of a type of poly hydroxyl alkyl phosphine-organic silicon tanning agent, including: add 10-100 parts of organic silicon into the reactor vessel, stir and heat up to 40-120'C, add 2-10 parts of surface active agent, continue stirring for 20-90min, control temperature at 40-120'C; add 10-300 20 parts of pure water, stir, and heat up to 40-90'C; add 500-1,500 parts of poly hydroxyl alkyl phosphine, continue stirring for 60-120min, adjust pH4-6; add 1-10 parts of stabilizer, stir for 30-60min; cool down to 20-50'C; take out from vessel. The invention also relates to a tanning fur process comprising the steps of: 1) Pre-treating the fur before pickling 25 2) Pickling at temperature 10-40'C, pH 2.5-3, for 18-48hr; 3) Tanning at 18-40'C, pH 3.0-5.0, adding poly hydroxyl alkyl phosphine-organic silicon tanning agent 2-8 gram/liter, tanning for 1-18 hr, every 1-8 hr successively; 4) Inspection at pH 5-7 and shrink temperature greater than 75'C, take out the skin; 4 WO 2009/105963 PCT/CN2009/000193 5) Fixing at temperature 20-50C, and, rotate 0.5-24 hr; 6) Reduction at temperature 45-65'C and rotate 1-8 hr; 7) Water washing boron plate drying, dry washing, tidying, dying; 8) Degreasing 5 9) Fur dyeing; and 10) Acid washing. Preferably the fur is woolskin or woolfell. In particular, the application of poly hydroxyl alkyl phosphine-organic silicon tanning agent in fur tanning includes the technique as follows: 10 1. Pre-treatment before pickling: use water of 20-40'C to wash, add 1 gram/liter of non-ion surface active agent, 0.2 gram/liter of methanoic acid, treat for 30-90 min; 2. Pickling: edible salt 60-70 gram/liter, temperature 10-40'C, water/feed ratio 1-60 kg/sheet, add methanoic acid 5 gram/liter, sulfuric acid 0.5 gram/liter, preservative 0.1 gram/liter, pH2.5-3, pickle for 18-48hr; 15 3. Tanning: edible salt 60 gram/liter, temperature 18-40 0 C, water/feed ratio 1-60 kg/sheet, add methanoic acid, sulfuric acid and sodium ethanoate, keep pH 3.0-5.0, add poly hydroxyl alkyl phosphine-organic silicon tanning agent 2-8 gram/liter, tan for 1-18 hr, every 1-8 hr successively add pure alkali 4-6 gram/liter, complete adding and continue stirring 1-8 hr; 20 4. Examination: at pH5-7 and shrink temperature greater than 75'C, take out the skin; 5. Fixing: water/feed ratio 1-60 kg/sheet, water temperature 20-50C, hydrogen peroxide 1-30 gram/liter, glycerol 0-10 gram/liter, Biquest 0.1-0.5 gram/liter, rotate 0.5-24 hr; 25 6. Reduction: water/feed ratio 1-60 kg/sheet, temperature 45-65'C, fur bleach powder 2-8 gram/liter, riquest 0-1 gram/liter, rotate 1-8 hr; 7. Water washing: water/feed ratio 1-60 kg/sheet, temperature 20-55'C, surface active agent 0-3 gram/liter, Briquest 0-1 gram/liter, acetic acid 0-1 gram/liter, rotate 10-30 min, boron plate drying, dry washing, tidying, dying; 5 WO 2009/105963 PCT/CN2009/000193 8. Degrease: water/feed ratio 1-60 kg/sheet, temperature 30-50'C, degrease agent 0.5-3 gram/sheet, pure alkali 0-2 gram/liter, immerse 30-60 min; 9. Fur dye: water/feed ratio 1-60 kg/sheet, temperature 55-70'C, even dye agent 0.2-2 gram/liter, ammonia water 0-2 gram/liter, rotate 10 min, add dye 0.1-3 gram/liter, 5 rotate 20-60 min, add methanoic acid 0.2-1 gram/liter, pH3-4, rotate 30 min, totally 2-5 times; 10. Acid washing: water/feed ratio 1-60 kg/sheet, room temperature, methanoic acid 0.2-1 gram/sheet, wash for 20 min, totally 2-4 times. That will do. Compared with the existing technology, this invention uses the mixture of poly 10 hydroxyl alkyl phosphine and organic silicon to make concurrent preparation. In the mean time, it chooses a special surface active agent with low destruction to fur indument and low damage to fur. The tanned fur is glossy, with high shrink temperature and bright color. The leather tolerates sweat and aging, with good toleration of dry/wet washing. The leather does not detan, with guaranteed durability, 15 tear strength and tensile strength. The wipe leather tanned by using the product of this invention has high water absorption and good wipe effect. It can produce pure white leather, and tolerate high temperature yellowing and light yellowing. The tanned leather is healthy, without toxic heavy metals such as chromium etc. The content of methyl aldehyde is lower than 20PPM, without other aldehydes such as pentane 20 dialdehyde etc. It also has good flame-retardant property. The waste of the finished product can degrade naturally or be treated with incineration. In the tanning technique, hazardous bactericides such as pentachlorophenol etc. are not used. Throughout the entire process of the leather-making and fur-making technique, degrease is entirely waterborne, the hazard of organic solvent to human body is thoroughly eliminated. The 25 application tanning technique has low temperature, short time, low energy consumption, and saves energy and protects environment. It can increase the absorption and fixing of dyestuff, decrease the use of dyestuff by 1/3, and decrease the chroma of the dye waste water. The tanning agent itself has low toxicity, and has no potential safety hazard within the applied range of concentration and pH. Its toxicity to 6 WO 2009/105963 PCT/CN2009/000193 aquatic animal is low. It can degrade naturally, with degradation half life 26-28 days. The tanning agent does not accumulate in the body of organism, and does not cause cancer, deform and genetic mutation. Its production technique is simple, easy to control and inspect. It can guarantee the stability and consistency of the product. 5 Embodiment of the Present Invention Further explanation of this invention with reference to embodiments is given below. Example 1: A kind of poly hydroxyl alkyl phosphine-organic silicon tanning agent composite Tetra hydroxyl methyl phosphorus chloride 500 kg, Amino silicon oil of molecular mass range 100 kg, 10,000-200,000 Dodecyl alcohol polyoxyethylene (3) ether 2 kg, (AEO-3) White sugar 10 kg and Pure water 10 kg. Example 2: A kind of poly hydroxyl alkyl phosphine-organic silicon tanning agent composite Tri hydroxyl alkyl phosphine 1,500 kg, Hydroxyl hydrogen-containing silicon oil of 10 kg, molecular mass range 10,000-200,000 Dodecyl alcohol polyoxyethylene (9) ether 10 kg, (AEO-9) Glycerol 1 kg and Pure water 300 kg. 7 WO 2009/105963 PCT/CN2009/000193 Example 3: A kind of poly hydroxyl alkyl phosphine-organic silicon tanning agent composite Tetra hydroxyl methyl phosphorus chloride 1,000 kg, Methyl silicon oil of molecular mass range 55 kg, 10,000-200,000 Dodecyl alcohol polyoxyethylene (10) ether 6 kg, (AEO-10) Tri ethanol amine 5.5 kg and Pure water 155 kg. Example 4: A kind of poly hydroxyl alkyl phosphine-organic silicon tanning agent composite Tri hydroxyl methyl phosphine 750 kg, Amino hydrogen-containing silicon oil of 30 kg, molecular mass range 10,000-200,000 Dodecyl alcohol polyoxyethylene (15) ether 8 kg, (AEO-15) Di ethanol amine 3 kg and Pure water 230 kg. Example 5: A kind of poly hydroxyl alkyl phosphine-organic silicon tanning agent composite Tetra hydroxyl methyl phosphorus chloride 1,300 kg, Hydroxyl silicon oil of molecular mass range 80 kg, 10,000-200,000 Dodecyl alchohol polyoxyethylene (20) ether 4 kg, (AEO-20) Mono ethanol amine 8 kg and Pure water 80 kg. 8 WO 2009/105963 PCT/CN2009/000193 Example 6: A kind of poly hydroxyl alkyl phosphine-organic silicon tanning agent composite Tr hydroxyl methyl phosphine 1,000 kg, Methyl hydrogen-containing silicon oil of 10 kg, molecular mass range 10,000-200,000 Dodecyl benzene sodium sulfonate 10 kg, Octadecyl alcohol 5.5 kg and Pure water 10 kg. Example 7: A type of poly hydroxyl alkyl phosphine-organic silicon tanning agent composite Tetra hydroxyl methyl phosphorus chloride 1,000 kg, Amino silicon oil of molecular mass range 100 kg, 10,000-200,000 Dodecyl sodium sulfate 2 kg, White sugar 5.5 kg and Pure water 300 kg. Example 8: A kind of poly hydroxyl alkyl phosphine-organic silicon tanning agent composite Tri hydroxyl methyl phosphine 1,500 kg, Hydroxyl hydrogen-containing silicon oil of 55 kg, molecular mass range 10,000-200,000 Imidazoline double-property surface active 2 kg, agent Glycerol 10 kg and Pure water 155 kg. 9 WO 2009/105963 PCT/CN2009/000193 Example 9: A kind of poly hydroxyl alkyl phosphine-organic silicon tanning agent composite Tetra hydroxyl methyl phosphorus chloride 500 kg, Methyl silicon oil of molecular mass range 55 kg, 10,000 to 200,000 Alkyl quaternary ammonium salt 10 kg, Tri ethanol amine 1 kg and Pure water 155 kg. Example 10: A kind of poly hydroxyl alkyl phosphine-organic silicon tanning agent composite Tri hydroxyl methyl phosphine 1,500 kg, Hydrogen-containing silicon oil of molecular 10 kg, mass range 10,000-200,000 Alkyl tertiary ammonium salt 6 kg, Di ethanol amine 10 kg and Pure water 10 kg. Example 11: A kind of poly hydroxyl alkyl phosphine-organic silicon tanning agent composite Tetra alkyl phosphorus chloride 500 kg, Silicon oil of molecular mass range 100 kg, 10,000-200,000 Alkyl amine polyoxyethylene (15) ether 6 kg, Mono ethanol amine 1 kg and Pure water 300 kg. Example 12: A kind of poly hydroxyl alkyl phosphine-organic silicon tanning agent composite 10 WO 2009/105963 PCT/CN2009/000193 Tri hydroxyl methyl phosphine 1,400 kg, Hydrogen-containing silicon oil of molecular 20 kg, mass 10,000-200,000 Alkyl alcohol polyoxyethylene ether sodium 8 kg, sulfate Octadecane alcohol 2kg and Pure water 250 kg. Example 13: A kind of poly hydroxyl alkyl phosphine-organic silicon tanning agent composite Tetra hydroxyl methyl phosphorus chloride 600 kg, Silicon oil of molecular mass range 90 kg, 10,000-200,000 Dodecyl alcohol polyoxyethylene (3) ether 2 kg, (AEO-3) Dodecyl alcohol polyoxyethylene (9) ether 1 kg, (AEO-9) Dodecyl benzene sodium sulfonate 1 kg, White sugar 8 kg and Pure water 30 kg. Example 14: Preparation of a kind of poly hydroxyl alkyl phosphine-organic silicon tanning agent According to what described in example 1, measure the component of the 5 composite, add the organic silicon into the reactor vessel, stir and heat up to 40'C, add in the surface active agent and continue stirring for 90min, control the temperature at 40'C. Add in pure water, stir, and cool down to 40'C. Add in poly hydroxyl alkyl phosphine, continue stirring for 120 min, and adjust pH6. Add in stabilizer, stir for 60 min. Cool down to 20'C. Take out from the vessel and that will do. I I WO 2009/105963 PCT/CN2009/000193 Example 15: Preparation of a kind of poly hydroxyl alkyl phosphine-organic tanning agent According to what described in example 15, measure the component of the 5 composite, add the organic silicon into the reactor vessel, stir and heat up to 120'C, add in the surface active agent and continue stirring for 20 min, control the temperature at 120'C. Add in pure water, stir, and cool down to 90'C. Add in poly hydroxyl alkyl phosphine, continue stirring for 60 min, and adjust pH4. Add in stabilizer, stir for 30 min. Cool down to 50'C. Take out from the vessel and that will do. 10 Example 16: Preparation of a kind of poly hydroxyl alkyl phosphine-organic silicon tanning agent According to what described in example 3, measure the component of the composite, add the organic silicon into the reactor vessel, stir and heat up to 80'C, add 15 in the surface active agent and continue stirring for 55min, control the temperature at 80'C. Add in pure water, stir, and cool down to 65'C. Add in poly hydroxyl alkyl phosphine, continue stirring for 90 min, and adjust pH5. Add in stabilizer, stir for 45 min. Cool down to 35'C. Take out from the vessel and that will do. 20 Example 17: Preparation of a kind of poly hydroxyl alkyl phosphine-organic silicon tanning agent According to what described in example 13, measure the component of the composite, add the organic silicon into the reactor vessel, stir and heat up to 90'C, add in the surface active agent composite and continue stirring for 40min, control the 25 temperature at 70'C. Add in pure water, stir, and cool down to 60'C. Add in poly hydroxyl alkyl phosphine, continue stirring for 100 min, and adjust pH5. Add in stabilizer, stir for 40 min. Cool down to 40 0 C. Take out from the vessel and that will do. 12 WO 2009/105963 PCT/CN2009/000193 Example 18: Application of a kind of poly hydroxyl alkyl phosphine-organic silicon tanning agent in fur tanning technique, including the following technique: 1. Pre-treatment before pickling: use water of 20'C to wash, add in 1 gram/liter of non-ion surface active agent, 0.2 gram/liter of methanoic acid, treat for 90 min; 5 2. Pickling: edible salt 60 gram/liter, temperature 40'C, water/feed ratio 1 kg/sheet, add methanoic acid 5 gram/liter, sulfuric acid 0.5 gram/liter, preservative 0.1 gram/liter, pH2.5-3 and pickle for 48hr; 3. Tanning: edible salt 60 gram/liter, temperature 18'C, water/feed ratio 60 kg/sheet, add methanoic acid, sulfuric acid and sodium methanoate, make pH 3.0-5.0, 10 add 2 gram/liter of the poly hydroxyl alkyl phosphine-organic silicon tanning agent described in example 14, tan for 18 hr, add 6 gram/liter of pure alkali successively in 1 hour, continue stirring for 1 hr after adding; 4. Inspection: at pH5-7 and shrink temperature greater than 75'C, take out the skin; 15 5. Fixing: water/feed ratio 60 kg/sheet, water temperature 20'C, hydrogen peroxide 30 gram/liter, Biquest 0.5 gram/liter, rotate 0.5 hr; 6. Reduction: water/feed ratio 60 kg/sheet, temperature 45'C, bleach fur powder 8 gram/liter, rotate for 8 hr; 7. Water washing: water/feed ratio 1 kg/sheet, temperature 55'C, Briquest 1 20 gram/liter, rotate for 30 min, boron plate drying, dry washing, tidying, dying; 8. Degrease: water/feed ratio 1 kg/sheet, temperature 50C, degrease agent 0.5 gram/liter, pure alkali 2 gram/liter, pickle for 30 min; 9. Fur dye: water/feed ratio 60 kg/sheet, temperature 55 0 C, even dye agent 2 gram/liter, rotate 10 min, add dyestuff 3 gram/liter, rotate for 20 min, add methanoic 25 acid 1 gram/liter, pH 3
-
4 , rotate 30 min, totally 2 times; 10. Acid washing: water/feed ratio 60 kg/sheet, room temperature, methanoic acid 0.2 gram/liter, wash for 20 min, totally 4 times, and that will do. Example 19: Application of a kind of poly hydroxyl alkyl phosphine-organic 13 WO 2009/105963 PCT/CN2009/000193 silicon tanning agent in fur tanning technique, including the following technique: 1. Pre-treatment before pickling: use water of 40'C to wash, add in 1 gram/liter of non-ion surface active agent, methanoic acid 0.2 gram/liter, treat for 30 min; 2. Pickling: edible salt 70 gram/liter, temperature I 0 0 C, water/feed ratio 60 5 kg/sheet, add methanoic acid 5 gram/liter, sulfuric acid 0.5 gram/liter, preservative 0.1 gram/liter, pH2.5-3 and pickle for 1 8hr; 3. Tanning: edible salt 60 gram/liter, temperature 40 C, water/feed ratio 1 kg/sheet, add methanoic acid, sulfuric acid and sodium methanoate, make pH 3.0-5.0, add 8 gram/liter of poly hydroxyl alkyl phosphine-organic silicon described in example 10 15, tan for lhr, add pure 4 gram/liter of pure alkali successively in 8 hours, and continue stirring for 8 hr after adding; 4. Inspection: at pH5-7 and shrink temperature greater than 75'C, take out the skin; 5. Fixing: water/feed ratio 1 kg/sheet, water temperature 50'C, hydrogen 15 peroxide 1 gram/liter, glycerol 10 gram/liter, Biquest 0.1 gram/liter, rotate for 24 hr; 6. Reduction: water/feed ratio 1 kg/sheet, temperature 65*C, bleach fur powder 2 gram/liter, riquest 1 gram/liter, rotate for lhr; 7. Water washing: water/feed ratio 60 kg/sheet, temperature 20'C, surface active agent 3 gram/liter, acetic acid 1 gram/liter, rotate for 10 min, boron plate drying, dry 20 washing, tidying, dying; 8. Degrease: water/feed ratio 60 kg/sheet, temperature 30'C, degrease agent 3 gram/liter, pickle for 60 min; 9. Fur dying: water/feed ratio 1 kg/sheet, temperature 70'C, even dye agent 0.2 kg/liter, ammonia water 2 gram/liter, rotate for 10 min, add dye 0.1 gram/liter, rotate 60 25 min, add methanoic acid 0.2 gram/liter, pH3-4, rotate 30 min, totally 5 times; 10. Acid washing: water/feed ratio 1 kg/sheet, room temperature, methanoic acid 1 gram/liter, wash for 20 min, totally 2 times, and that will do. Example 20: Application of a kind of poly hydroxyl alkyl phosphine-organic 14 WO 2009/105963 PCT/CN2009/000193 silicon tanning agent in fur tanning technique, including the following technique: 1. Pre-treatment before pickling: use water of 30'C to wash, add in non-ion surface active agent 1 gram/liter, methanoic acid 0.2 gram/liter, treat for 60 min; 2. Pickling: edible salt 65 gram/liter, temperature 25'C, water/feed ratio 30 5 kg/sheet, add methanoic acid 5 gram/liter, sulfuric acid 0.5 gram/liter, preservative 0.1 gram/liter, pH2.5-3 and pickle for 33hr; 3. Tanning: edible salt 60 gram/liter, temperature 29'C, water/feed ratio 30 kg/sheet, add methanoic acid, sulfuric acid and sodium methanoate, make pH 3.0-5.0, add 5 gram/liter of the poly hydroxyl alkyl phosphine-organic silicon tanning agent 10 described in example 16, tan for 9 hr, add 5 gram/liter of pure alkali successively in 4 hours, and continue stirring for 5hr after adding; 4. Inspection: at pH5-7 and shrink temperature greater than 75'C, take out the skin; 5. Fixing: water/feed ratio 30 kg/sheet, water temperature 35 C, hydrogen 15 peroxide 15 gram/liter, glycerol 50 gram/liter, Biquest 0.3 gram/liter, rotate 12hr; 6. Reduction: water/feed ratio 30 kg/sheet, temperature 55'C, bleach fur powder 5 gram/liter, riquest 0.5 gram/liter, rotate for 4 hr; 7. Water washing: water/feed ratio 30 kg/sheet, temperature 37'C, surface active agent 1.5 gram/liter, Briquest 0.5 gram/liter, acetic acid 0.5 gram/liter, rotate for 20 min, 20 boron plate drying, dry cleaning, tidying, dying; 8. Degrease: water/feed ratio 30 kg/sheet, temperature 40'C, degrease agent 2 gram/liter, pure alkali 1 gram/liter, pickle for 45 min; 9. Fur dye: water/feed ratio 30 kg/sheet, temperature 60'C, even dye agent 1 gram/liter, ammonia water 1 gram/liter, rotate 10 min, add dyestuff 1.5 gram/liter, 25 rotate 40 min, add methanoic acid 0.6 gram/liter, pH3-4, rotate 30 min, totally 4 times; 10. Acid washing: water/feed ratio 30 kg/sheet, room temperature, acetic acid 0.6 gram/liter, wash for 20 min, totally 3 times, and that will do. Example 21: Application of a kind of poly hydroxyl alkyl phosphine-organic 15 WO 2009/105963 PCT/CN2009/000193 silicon tanning agent in fur tanning technique, including the following technique: 1. Pre-treatment before pickling: use water of 35'C to wash, add in non-ion surface active agent 1 gram/liter, methanoic acid 0.2 gram/liter, treat for 50 min; 2. Pickling: edible salt 66 gram/liter, temperature 30'C, water/feed ratio 40 5 kg/sheet, add methanoic acid 5 gram/liter, sulfuric acid 0.5 gram/liter, preservative 0.1 gram/liter, pH2.5-3 and pickle for 30hr; 3. Tanning: edible salt 60 gram/liter, temperature 25'C, water/feed ratio 25 kg/sheet, add methanoic acid, sulfuric acid and sodium methanoate, make pH 3.0-5.0, add 5 gram/liter of pure alkali successively in 5 hours, and continue stirring for 4 hr 10 after adding; 4. Inspection: at pH5-7 and shrink temperature greater than 75'C and take out the skin; 5. Fixing: water/feed ratio 35 kg/sheet, water temperature 30'C, hydrogen peroxide 16 gram/liter, glycerol 4 gram/liter, Biquest 0.4 gram/liter, rotate for 13 hr; 15 6. Reduction: water/feed ratio 31 kg/sheet, temperature 550, bleach fur powder 5 gram/liter, riquest 0.6 gram/liter, rotate 5 hr; 7. Water washing: water/feed ratio 25 kg/sheet, temperature 35'C, surface active agent 2 gram/liter, Briquest 0.4 gram/liter, acetic acid 0.6 gram/liter, rotate 20min, boron plate drying, dry washing, tidying, dying; 20 8. Degrease: water/feed ratio 34 kg/sheet, temperature 40'C, degrease agent 1.8 gram/liter, pure alkali 1 gram/liter, pickle for 45min; 9. Fur dye: water/feed ratio 30 kg/sheet, temperature 60'C, even dye agent 1.1 gram/liter, ammonia water 1 gram/liter, rotate 10 min, add dye 1.6 gram/liter, rotate 40 min, add methanoic acid 0.6 gram/liter, pH3-4, rotate 30 min, totally 3 times; 25 10. Acid washing: water/feed ratio 32 kg/sheet, room temperature, methanoic acid 0.5 gram/liter, wash for 20 min, totally 3 times, and that will do. Example 22: Fur damage experiment of a kind of poly hydroxyl alkyl phosphine-organic silicon tanning agent 16 WO 2009/105963 PCT/CN2009/000193 Patent CN10711956 product A and a kind of poly hydroxyl alkyl-organic silicon tanning agent W of example 1 follow the same technique flow to produce sheep shearing leather, and measure the alkali dissolution of wool. Technique flow: pickle skin - tan - oxidize - reduce - dry. Take the wool of 5 symmetric part after drying and the pickled raw material skin to measure the alkali dissolution. Experiment method: take a sheep skin, make circular mark along the backbone line, and take down the fur, dry it, measure the alkali dissolution. In the mean time, follow the aforesaid technique flow to perform comparative study of A and W 10 Experiment record: The pickled skin, lamb skin, is the major product manufactured by factory. It originates from Longfeng Leather and Fur LLC of Jiaozuo, Henan. Equipment: paddle vat Tanning: feed ratio = 50 kg water / sheet of skin, temperature 20 degree 15 Edible salt 60 gram/liter Methanoic acid 0.5 gram/liter Briquest 301-50A 1 gram/liter, rotate 30 minutes, pH4.5 A or B 6 gram/liter, rotate 240 minutes Pure alkali 4 gram/liter, rotate 240 minutes (add successively, interval 30 20 minutes) Water washing: room temperature water washing 10 minutes Drying-sampling-measure the alkali dissolution of ship skin. As for the measurement method, ISO method is followed for measurement. The fur sampling point of is near the circular mark. Fur sampling is based on the 25 symmetric position of skin sheet. Measurement result: The wool alkali dissolution degrees of application product A and tanned finished wool leather are 25% and 17% respectively. Experiment Result: Utilize W to tan wool leather, the damage rate of wool is (17-15) /15=13.33% 17 WO 2009/105963 PCT/CN2009/000193 Utilize A to tan wool leather, the damage rate of wool is (25-15) /15=66.67% This experiment proves that product W of this invention can decrease the rate of wool damage by up to 53.33%. 5 Example 23: Dye function experiment of a kind of poly hydroxyl alkyl phosphine-organic silicon tanning agent Application Example: Production of New Zealand long-wool sheep skin. Raw Material Skin: New Zealand saline lamb skin, with complete skin pattern, no knife cut hollow, and no significant pollution on the skin plate. 10 Tanning Equipment: stainless steel or glass steel paddle vat Liquid Coefficient: 50 kg water/sheet of skin Production Technique: technique described in example 18. Result: even dye. 15 Example 24: Toxicology Experiment Acute Toxicity: inhale through respiration LC50 (rat) 5.55mg/litre/4h. Through mouth LD50(rat)575mg/kg Skin LD50 (rat) >2000mg/kg Sub-acute and Chronic Toxicity: 20 Stimulation: - nose, throat and respiratory system, not causing significant stimulus -skin, single-layered paste by means of "semi-occlusive" on rabbit skin for 4 hours causes minimum degree of stimulation. Chronic Toxicity/Carcinogenicity: For rats (both gender) F344/N and B6C3F1 25 fed with 5 or 1 OmgTHPS for 2 years, no carcinogenicity is found. Mutagenicity: Bacterial mutagen (Ames) - negative This product does not cause disorder synthesis of DNA. The major fatality analysis on living body of rat shows negative result. is WO 2009/105963 PCT/CN2009/000193 Toxicity recurrence/development: after the study on rat and rabbit, with the existence of obvious original toxicity, there is no recurrence of toxicity. For rate experiment, at the dosage of 15mg/kg weight, no effect level of toxicity development is observed. 5 For rabbit experiment, at the dosage of 18mg/kg weight, no effect level of toxicity development is observed. Example 25: Ecology Experiment General View of Ecology: If the product enters the water zone, it does not cause 10 significant adverse effect to the environment. Mobility: This product is water soluble. Durability/degradability: In the presence of excess oxygen, it is easy for the product to biodegrade and precipitate in the water system. In 28 days, it achieves 60% biodegradation. 15 Under anaerobic condition, it is easy for the product to biodegrade and precipitate in the water system. In 30 days, it achieves 80% biodegradation. Eco Toxicity: Subject rainbow trout to experiment for 96 hours, at dosage 119mg/litre, LC50; Subject big fins scale gills sunfish to experiment for 96 hours, at dosage 20 93mg/litre, LC50; Subject Daphnia magna to experiment for 48 hours, at dosage 19.4mg/litre, EC50; Subject wild duck to experiment, at dosage 11 3mg/KQ LD50; Subject brown shrimp to experiment for 96 hours, at dosage 340mg/litre, LC50; 25 Subject juvenile plaice to experiment for 96 hours, at dosage 86mg/litre, LC50; Subject Corophium Volutator to experiment for 10 hours, at dosage 2,174mg/KG (dry sediment weight), LC50. 19