CN101831024A - Method for preparing polymer retanning fat-liquoring agent and retanning fat-liquoring agent - Google Patents
Method for preparing polymer retanning fat-liquoring agent and retanning fat-liquoring agent Download PDFInfo
- Publication number
- CN101831024A CN101831024A CN 201010175187 CN201010175187A CN101831024A CN 101831024 A CN101831024 A CN 101831024A CN 201010175187 CN201010175187 CN 201010175187 CN 201010175187 A CN201010175187 A CN 201010175187A CN 101831024 A CN101831024 A CN 101831024A
- Authority
- CN
- China
- Prior art keywords
- long chain
- aliphatic alcohol
- chain aliphatic
- methacrylic acid
- toxilic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a method for preparing a polymer retanning fat-liquoring agent and the retanning fat-liquoring agent. The preparation method comprises the following steps of: preparing long-chain fatty alcohol maleic acid monoester by adopting C8-C18 long-chain fatty alcohol and maleic anhydride, preparing the long-chain fatty alcohol maleic acid monoester into long-chain fatty alcohol maleic acid monoester salt, and then dripping methacrylic acid octadecyl ester, aqueous solution of sodium methacrylate and aqueous solution of initiator into the long-chain fatty alcohol maleic acid monoester salt to perform aqueous emulsion copolymerization to form the polymer retanning fat-liquoring agent. The polymer retanning fat-liquoring agent contains terpolymer of the methacrylic acid octadecyl ester, the long-chain fatty alcohol maleic acid monoester and the methacrylic acid. The preparation method saves an organic solvent during synthesizing the retanning fat-liquoring agent so as to reduce environmental pollution, and meanwhile overcomes the defect of insufficient fat-liquoring performance of a long-chain fatty alcohol maleic acid monoester and methacrylic acid copolymer by introducing oleophilic methacrylic acid octadecyl ester monomer into the polymer.
Description
Technical field
The invention belongs to the leather chemical industry technical field, the preparation method who relates to a kind of polymer retanning fat-liquoring agent, the invention still further relates to the composite tan fatting agent that utilizes this method to make, contain methacrylic acid stearyl-long chain aliphatic alcohol toxilic acid monoesters-methacrylic acid ter-polymer in this composite tan fatting agent.
Background technology
Polymer retanning fat-liquoring agent has multi-functionals such as retanning, stuffing, waterproof and high associativity (water-fast wash, low haze value), be applied to leather production as a kind of high-grade leather chemical industry material, can shorten the process hides operation, reduce the skin material consumption, reduce the pollution of leather-making waste water environment.Polymer retanning fat-liquoring agent is a kind of amphiphilic structure macromolecular compound, by double bond containing chain alkyl is that lipophilicity monomer (as methacrylic acid stearyl and long chain aliphatic alcohol toxilic acid monoesters) obtains by free radical copolymerization with carboxylic hydrophilic monomer (as methacrylic acid and vinylformic acid), lipophilic group wherein has lubrication to leather fiber, play the stuffing effect, carboxyl on the hydrophilic monomer can with the chromium complexing in the leather fiber, play the retanning effect.Can adjust the retanning and the stuffing effect of polymkeric substance in theory by the ratio of adjusting oleophylic monomer and hydrophilic monomer.
Long chain aliphatic alcohol toxilic acid monoesters and methacrylic acid stearyl are two kinds of main lipophilicity monomers that are used to prepare polymer retanning fat-liquoring agent; the methacrylic acid stearyl is water insoluble; must in organic solvent, carry out copolymerization with (methyl) vinylformic acid, on synthesis technique, not meet requirement on environmental protection.Long chain aliphatic alcohol toxilic acid monoesters is compared with the methacrylic acid stearyl; the carboxyl of possess hydrophilic property on the molecule; can carry out aqueous emulsion polymerization with (methyl) vinylformic acid, not use or on a small quantity with an organic solvent, on synthesis technique, more meet requirement on environmental protection.The retanning fillibility of the multipolymer of long chain aliphatic alcohol toxilic acid monoesters and methacrylic acid is good, but this multipolymer be that the composite tan fatting agent that raw material obtains is compared with the methacrylic acid stearyl, the stuffing poor-performing.
Summary of the invention
In order to overcome above-mentioned problems of the prior art, the purpose of this invention is to provide a kind of preparation method of polymer retanning fat-liquoring agent, in the building-up process of fatting agent, need not with an organic solvent to meet requirement on environmental protection.
Another object of the present invention provides a kind of polymer retanning fat-liquoring agent that utilizes aforesaid method to make, and not only has good retanning fillibility, and has stuffing performance preferably.
The technical solution adopted in the present invention is, a kind of preparation method of polymer retanning fat-liquoring agent, adopt long chain aliphatic alcohol toxilic acid monoesters, methacrylic acid stearyl and methacrylic acid to carry out the water miscible liquid copolymerization and prepare polymer retanning fat-liquoring agent, this preparation method, carry out according to the following steps:
Step 1: 1: 1.05 in molar ratio～1.1, get C8～pure and mild maleic anhydride of C18 long-chain fat respectively, long chain aliphatic alcohol is warming up to 70 ℃～75 ℃, add maleic anhydride, mix, then, be warming up to 90 ℃～110 ℃, insulation reaction 2h～5h, synthetic long chain aliphatic alcohol toxilic acid monoesters;
Step 2: synthetic long chain aliphatic alcohol toxilic acid monoesters in the step 1 is cooled to 60 ℃～65 ℃, add deionized water, the mass ratio of deionized water and long chain aliphatic alcohol toxilic acid monoesters is 1～2: 1, stir 10min～20min, then, basic cpd is splashed in 25min～30min in the long chain aliphatic alcohol toxilic acid monoesters that adds deionized water, and the feasible pH value that adds the long chain aliphatic alcohol toxilic acid monoesters of deionized water is 7.0～7.5, obtains long chain aliphatic alcohol toxilic acid monoester salt;
Step 3: press mass ratio 1～2: 1, fetch water and methacrylic acid the dilute with water methacrylic acid respectively, then, with massfraction is in the methacrylic acid after 30% aqueous sodium hydroxide solution adds dilution, makes the pH value and be 6.5～7.0 methacrylic acid sodium water solution
Get initiator, this initiator is dissolved in the water, make the initiator solution of mass concentration 20～30%;
Step 4: get the methacrylic acid stearyl respectively, the long chain aliphatic alcohol toxilic acid monoester salt that step 2 makes, methacrylic acid sodium water solution and initiator solution that step 3 makes, the control initiator radical is 2%～10% in the massfraction of comonomer total mass, in the long chain aliphatic alcohol toxilic acid monoester salt in long chain aliphatic alcohol toxilic acid monoesters and the methacrylic aqueous acid mol ratio of methacrylic acid be 1: 1～3, the mol ratio of long chain aliphatic alcohol toxilic acid monoesters and methacrylic acid stearyl is 1: 0.2～1.0 in the long chain aliphatic alcohol toxilic acid monoester salt, long chain aliphatic alcohol toxilic acid monoester salt is warming up to 75 ℃～90 ℃, with the methacrylic acid stearyl, methacrylic acid sodium water solution and initiator solution splash into respectively in 1h～3h in the long chain aliphatic alcohol toxilic acid monoester salt after the intensification, then, under 75 ℃～90 ℃ temperature, react 1.5h～3h, after reaction is finished, reaction product is cooled to 60～65 ℃, add deionized water then, make polymer retanning fat-liquoring agent.
Another technical scheme of the present invention is, utilizes above-mentioned preparation method to make polymer retanning fat-liquoring agent, and this fatting agent is long chain aliphatic alcohol toxilic acid monoesters-methacrylic acid stearyl-methacrylic acid ter-polymers.
The preparation method of polymer retanning fat-liquoring agent of the present invention; adopt long chain aliphatic alcohol toxilic acid monoesters and methacrylic acid stearyl and methacrylic acid to carry out the water miscible liquid copolymerization; obtain long chain aliphatic alcohol toxilic acid monoesters-methacrylic acid stearyl-methacrylic acid ter-polymer composite tan fatting agent; in the preparation process; not with an organic solvent, do not meet requirement on environmental protection.The fatting agent that makes is long chain aliphatic alcohol toxilic acid monoesters-methacrylic acid stearyl-methacrylic acid ter-polymers, it is the amphiphilic macromolecule compound that contains hydrophilic radical carboxyl and lipophilic group alkyl group on a kind of molecule, dual-use function with retanning and stuffing, simultaneously, can also give the finished leather waterproof and water-fastly multiple function such as wash
Embodiment
The present invention is described in detail below in conjunction with embodiment.
Long chain aliphatic alcohol toxilic acid monoesters is a kind of emulsifying agent with reactive behavior, and the inventive method employing long chain aliphatic alcohol toxilic acid monoesters, methacrylic acid stearyl and methacrylic acid carry out the water miscible liquid copolymerization and prepare polymer retanning fat-liquoring agent.This preparation method, carry out according to the following steps:
Step 1: 1: 1.05 in molar ratio～1.1, get C8～pure and mild maleic anhydride of C18 long-chain fat respectively, this long chain aliphatic alcohol is warming up to 70～75 ℃, add maleic anhydride, mix, then, be warming up to 90～110 ℃, insulation reaction 2～5h, synthetic long chain aliphatic alcohol toxilic acid monoesters;
Step 2: synthetic long chain aliphatic alcohol toxilic acid monoesters in the step 1 is cooled to 60～65 ℃, add deionized water, the mass ratio of control deionized water and long chain aliphatic alcohol toxilic acid monoesters is 1～2: 1, stir 10～20min, then, basic cpd is splashed in 25～30min in the long chain aliphatic alcohol toxilic acid monoesters that adds deionized water, and the feasible pH value that adds the long chain aliphatic alcohol toxilic acid monoesters of deionized water is 7.0～7.5, obtains long chain aliphatic alcohol toxilic acid monoester salt;
It is that 30% aqueous sodium hydroxide solution or massfraction are 30% potassium hydroxide aqueous solution that basic cpd adopts ammoniacal liquor, massfraction.
Step 3: press mass ratio 1～2: 1, fetch water and methacrylic acid the dilute with water methacrylic acid respectively, then, with massfraction is in the methacrylic acid after 30% aqueous sodium hydroxide solution adds dilution, makes the pH value and be 6.5～7.0 methacrylic acid sodium water solution
Get initiator, this initiator is dissolved in the water, make the initiator solution of mass concentration 20～30%;
Initiator adopts a kind of in Sodium Persulfate, Potassium Persulphate or the ammonium persulphate, perhaps two kinds of combinations, and perhaps three's combination when adopting two kinds of combinations or three kinds of combinations, can be arbitrary proportion between the each component.
Step 4: get the methacrylic acid stearyl respectively, the long chain aliphatic alcohol toxilic acid monoester salt that step 2 makes, methacrylic acid sodium water solution and initiator solution that step 3 makes, the control initiator radical is 2～10% in the massfraction of comonomer total mass, preferred 5～8%, in the long chain aliphatic alcohol toxilic acid monoester salt in long chain aliphatic alcohol toxilic acid monoesters and the methacrylic aqueous acid mol ratio of methacrylic acid be 1: 1～3, preferred 1: 1.5～2.0, the mol ratio of long chain aliphatic alcohol toxilic acid monoesters and methacrylic acid stearyl is 1: 0.2～1.0 in the long chain aliphatic alcohol toxilic acid monoester salt, preferred 1: 0.4～0.6, long chain aliphatic alcohol toxilic acid monoester salt is warming up to 75～90 ℃, with the methacrylic acid stearyl, methacrylic acid sodium water solution and initiator solution splash into respectively in 1～3h in the long chain aliphatic alcohol toxilic acid monoester salt after the intensification, then, under 75～90 ℃ temperature of reaction, preferred 80～85 ℃, carry out polyreaction, reaction times is 1.5～3h, preferred 2.0～2.5h, after reaction is finished, reaction product is cooled to 60～65 ℃, add deionized water then, make polymer retanning fat-liquoring agent, the massfraction of controlling water in this polymer retanning fat-liquoring agent is 55～60%.
The polymer retanning fat-liquoring agent that adopts above-mentioned preparation method to make is long chain aliphatic alcohol toxilic acid monoesters-methacrylic acid stearyl-methacrylic acid ter-polymers.This ter-polymers is the amphiphilic structure macromolecular compound that contains hydrophilic radical carboxyl and lipophilic group chain alkyl on a kind of molecule, use it for leather processing, can play the dual-use function of retanning and oiling, simultaneously, giving the finished leather waterproof and water-fastly multiple performance such as wash, is a kind of multifunctional leather chemical materials.
Preparation method of the present invention is the lipophilicity monomer with long chain aliphatic alcohol toxilic acid monoesters and methacrylic acid stearyl, carry out the water miscible liquid copolymerization with methacrylic acid and prepare polymer retanning fat-liquoring agent, long chain aliphatic alcohol toxilic acid monoesters wherein is the lipophilicity monomer in the polyreaction, it also is the emulsifying agent in the polyreaction, make the inventive method in the building-up process of composite tan fatting agent, need not with an organic solvent, reduced pollution to environment, simultaneously oil loving monomer methacrylic acid stearyl is introduced in the polymkeric substance, improved long chain aliphatic alcohol toxilic acid monoesters and the insufficient shortcoming of Sipacril 2739OF stuffing performance.
Contain oil loving chain alkyl and hydrophilic carboxyl on the molecule of polymer retanning fat-liquoring agent of the present invention, wherein chain alkyl has lubrication to leather fiber, can play the function of stuffing, carboxyl can combine with leather fiber, play the function of retanning, therefore composite tan fatting agent of the present invention is a kind of functional type material with stuffing and retanning two-fold function, be used for leather production, have retanning, stuffing, waterproof and water-fastly multiple function such as wash, can reduce the consumption of leather chemical industry material, reduction process hides operation helps to realize the production that cleans of leather.
Embodiment 1
1: 1.05 in molar ratio, get the pure and mild maleic anhydride of C8 long-chain fat respectively, the C8 long chain aliphatic alcohol is warming up to 70 ℃, add maleic anhydride, mix, then, be warming up to 90 ℃, insulation reaction 5h, synthetic C8 long chain aliphatic alcohol toxilic acid monoesters; Synthetic C8 long chain aliphatic alcohol toxilic acid monoesters is cooled to 60 ℃, add deionized water, the mass ratio of deionized water and this C8 long chain aliphatic alcohol toxilic acid monoesters is 1: 1, stir 10min, then, ammoniacal liquor is splashed in 25～30min in the C8 long chain aliphatic alcohol toxilic acid monoesters that adds deionized water, and the feasible pH value that adds the C8 long chain aliphatic alcohol toxilic acid monoesters of deionized water is 7.0, obtains C8 long chain aliphatic alcohol toxilic acid monoester salt; Pressed mass ratio 1: 1, fetch water respectively and methacrylic acid, the dilute with water methacrylic acid, then, with massfraction is in the methacrylic acid after 30% aqueous sodium hydroxide solution adds dilution, obtain the pH value and be 6.5 methacrylic acid sodium water solution, Sodium Persulfate is dissolved in water, make the initiator solution of mass concentration 20%; Get the methacrylic acid stearyl respectively, the C8 long chain aliphatic alcohol toxilic acid monoester salt that makes, methacrylic acid sodium water solution and initiator solution, the control initiator radical is 2% in the massfraction of comonomer total mass, in the C8 long chain aliphatic alcohol toxilic acid monoester salt in C8 long chain aliphatic alcohol toxilic acid monoesters and the methacrylic aqueous acid mol ratio of methacrylic acid be 1: 1, the mol ratio of C8 long chain aliphatic alcohol toxilic acid monoesters and methacrylic acid stearyl is 1: 0.2 in the C8 long chain aliphatic alcohol toxilic acid monoester salt, C8 long chain aliphatic alcohol toxilic acid monoester salt is warming up to 75 ℃, with the methacrylic acid stearyl, methacrylic aqueous acid and initiator solution splash into respectively in 1～3h in the C8 long chain aliphatic alcohol toxilic acid monoester salt after the intensification, then, polyreaction 3h under 75 ℃ temperature of reaction, after reaction is finished, reaction product is cooled to 60 ℃, add deionized water then, the massfraction that makes water is 60% polymer retanning fat-liquoring agent.
Embodiment 2
1: 1.1 in molar ratio, get the pure and mild maleic anhydride of long-chain fat of C18 respectively, the C18 long chain aliphatic alcohol is warming up to 75 ℃, add maleic anhydride, mix, then, be warming up to 110 ℃, insulation reaction 2h, synthetic C18 long chain aliphatic alcohol toxilic acid monoesters; Synthetic C18 long chain aliphatic alcohol toxilic acid monoesters is cooled to 65 ℃, add deionized water, the mass ratio of deionized water and C18 long chain aliphatic alcohol toxilic acid monoesters is 2: 1, stir 20min, then, with massfraction is that 30% aqueous sodium hydroxide solution splashes in 25～30min in the C18 long chain aliphatic alcohol toxilic acid monoesters that adds deionized water, makes that the pH value of the C18 long chain aliphatic alcohol toxilic acid monoesters that adds deionized water is 7.5, obtains C18 long chain aliphatic alcohol toxilic acid monoester salt; Pressed mass ratio 2: 1, fetch water respectively and methacrylic acid, the dilute with water methacrylic acid, then, with massfraction is in the methacrylic acid after 30% aqueous sodium hydroxide solution adds dilution, make the pH value and be 7.0 methacrylic acid sodium water solution, Potassium Persulphate is dissolved in the water, make the initiator solution of mass concentration 25%; Get the methacrylic acid stearyl respectively, the C18 long chain aliphatic alcohol toxilic acid monoester salt that makes, methacrylic acid sodium water solution and initiator solution, the control initiator radical is 10% in the massfraction of comonomer total mass, in the C18 long chain aliphatic alcohol toxilic acid monoester salt in C18 long chain aliphatic alcohol toxilic acid monoesters and the methacrylic aqueous acid mol ratio of methacrylic acid be 1: 3, the mol ratio of C18 long chain aliphatic alcohol toxilic acid monoesters and methacrylic acid stearyl is 1: 1.0 in the C18 long chain aliphatic alcohol toxilic acid monoester salt, C18 long chain aliphatic alcohol toxilic acid monoester salt is warming up to 90 ℃, with the methacrylic acid stearyl, methacrylic aqueous acid and initiator solution splash into respectively in 1～3h in the C18 long chain aliphatic alcohol toxilic acid monoester salt after the intensification, then, polyreaction 1.5h under 90 ℃ temperature, after reaction is finished, reaction product is cooled to 65 ℃, add deionized water then, the massfraction that makes water is 55% polymer retanning fat-liquoring agent.
Embodiment 3
1: 1.075 in molar ratio, get the pure and mild maleic anhydride of C13 long-chain fat respectively, the C13 long chain aliphatic alcohol is warming up to 72.5 ℃, add maleic anhydride, mix, then, be warming up to 100 ℃, insulation reaction 3.5h, synthetic C13 long chain aliphatic alcohol toxilic acid monoesters; Synthetic C13 long chain aliphatic alcohol toxilic acid monoesters is cooled to 62.5 ℃, add deionized water, the mass ratio of deionized water and C13 long chain aliphatic alcohol toxilic acid monoesters 1.5: 1, stir 15min, then, with massfraction is that 30% potassium hydroxide aqueous solution splashes in 25～30min in the long chain aliphatic alcohol toxilic acid monoesters that adds deionized water, makes that the pH value of the C13 long chain aliphatic alcohol toxilic acid monoesters that adds deionized water is 7.25, obtains C13 long chain aliphatic alcohol toxilic acid monoester salt; Pressed mass ratio 1.5: 1, fetch water respectively and methacrylic acid, the dilute with water methacrylic acid, then, with massfraction is in the methacrylic acid after 30% aqueous sodium hydroxide solution adds dilution, obtain the pH value and be 6.75 methacrylic acid sodium water solution, ammonium persulphate is dissolved in the water, make the initiator solution of mass concentration 30%; Get the methacrylic acid stearyl respectively, the C13 long chain aliphatic alcohol toxilic acid monoester salt that makes, methacrylic acid sodium water solution and initiator solution, the control initiator radical is 6% in the massfraction of comonomer total mass, in the C13 long chain aliphatic alcohol toxilic acid monoester salt in C13 long chain aliphatic alcohol toxilic acid monoesters and the methacrylic aqueous acid mol ratio of methacrylic acid be 1: 2, the mol ratio of C13 long chain aliphatic alcohol toxilic acid monoesters and methacrylic acid stearyl is 1: 0.6 in the C13 long chain aliphatic alcohol toxilic acid monoester salt, C13 long chain aliphatic alcohol toxilic acid monoester salt is warming up to 82.5 ℃, with the methacrylic acid stearyl, methacrylic aqueous acid and initiator solution splash into respectively in 1～3h in the C13 long chain aliphatic alcohol toxilic acid monoester salt after the intensification, then, polyreaction 2.25h under 82.5 ℃ temperature, after reaction is finished, reaction product is cooled to 62.5 ℃, add deionized water then, the massfraction that makes water is 58% polymer retanning fat-liquoring agent.
Embodiment 4
1: 1.06 in molar ratio, get the pure and mild maleic anhydride of C10 long-chain fat respectively, the C10 long chain aliphatic alcohol is warming up to 71 ℃, add maleic anhydride, mix, then, be warming up to 95 ℃, insulation reaction 4.5h, synthetic C10 long chain aliphatic alcohol toxilic acid monoesters; Synthetic C10 long chain aliphatic alcohol toxilic acid monoesters is cooled to 61 ℃, add deionized water, the mass ratio of deionized water and C10 long chain aliphatic alcohol toxilic acid monoesters is 1.1: 1, stir 11min, then, ammoniacal liquor is splashed in 25～30min in the C10 long chain aliphatic alcohol toxilic acid monoesters that adds deionized water, and the feasible pH value that adds the C10 long chain aliphatic alcohol toxilic acid monoesters of deionized water is 7.1, obtains C10 long chain aliphatic alcohol toxilic acid monoester salt; Pressed mass ratio 1.8: 1, fetch water respectively and methacrylic acid, the dilute with water methacrylic acid, then, with massfraction is in the methacrylic acid after 30% aqueous sodium hydroxide solution adds dilution, obtain the pH value and be 6.6 methacrylic acid sodium water solution, the Sodium Persulfate and the Potassium Persulphate of arbitrary proportion is dissolved in the water, make the initiator solution of mass concentration 22%; Get the methacrylic acid stearyl respectively, C10 long chain aliphatic alcohol toxilic acid monoester salt, methacrylic acid sodium water solution and initiator solution, the control initiator radical is 3% in the massfraction of comonomer total mass, in the C10 long chain aliphatic alcohol toxilic acid monoester salt in C10 long chain aliphatic alcohol toxilic acid monoesters and the methacrylic aqueous acid mol ratio of methacrylic acid be 1: 1.5, the mol ratio of C10 long chain aliphatic alcohol toxilic acid monoesters and methacrylic acid stearyl is 1: 0.4 in the C10 long chain aliphatic alcohol toxilic acid monoester salt, C10 long chain aliphatic alcohol toxilic acid monoester salt is warming up to 80 ℃, with the methacrylic acid stearyl, methacrylic aqueous acid and initiator solution splash into respectively in 1～3h in the C10 long chain aliphatic alcohol toxilic acid monoester salt, then, polyreaction 2h under 80 ℃ temperature, after reaction is finished, reaction product is cooled to 64 ℃, add deionized water then, the massfraction that makes water is 56% polymer retanning fat-liquoring agent.
Embodiment 5
1: 1.08 in molar ratio, get the pure and mild maleic anhydride of C16 long-chain fat respectively, the C16 long chain aliphatic alcohol is warming up to 74 ℃, add maleic anhydride, mix, then, be warming up to 105 ℃, insulation reaction 2.5h, synthetic C16 long chain aliphatic alcohol toxilic acid monoesters; Synthetic C16 long chain aliphatic alcohol toxilic acid monoesters is cooled to 64 ℃, add deionized water, the mass ratio of deionized water and C16 long chain aliphatic alcohol toxilic acid monoesters is 1.9: 1, stir 18min, with massfraction is that 30% aqueous sodium hydroxide solution splashes in 25～30min in the C16 long chain aliphatic alcohol toxilic acid monoesters that adds deionized water, the feasible pH value that adds the C16 long chain aliphatic alcohol toxilic acid monoesters of deionized water is 7.4, obtains C16 long chain aliphatic alcohol toxilic acid monoester salt; Pressed quality 1.1: 1, fetch water respectively and methacrylic acid, the dilute with water methacrylic acid, then, with massfraction is in the methacrylic acid after 30% aqueous sodium hydroxide solution adds dilution, make the pH value and be 6.9 methacrylic acid sodium water solution, the Potassium Persulphate and the ammonium persulphate of arbitrary proportion is dissolved in the water, make the initiator solution of mass concentration 28%; Get the methacrylic acid stearyl respectively, C16 long chain aliphatic alcohol toxilic acid monoester salt, methacrylic acid sodium water solution and initiator solution, the control initiator radical is 8% in the massfraction of comonomer total mass, in the C16 long chain aliphatic alcohol toxilic acid monoester salt in C16 long chain aliphatic alcohol toxilic acid monoesters and the methacrylic aqueous acid mol ratio of methacrylic acid be 1: 1.75, the mol ratio of C16 long chain aliphatic alcohol toxilic acid monoesters and methacrylic acid stearyl is 1: 0.5 in the C16 long chain aliphatic alcohol toxilic acid monoester salt, C16 long chain aliphatic alcohol toxilic acid monoester salt is warming up to 85 ℃, with the methacrylic acid stearyl, methacrylic acid sodium water solution and initiator solution splash into respectively in 1～3h in the C16 long chain aliphatic alcohol toxilic acid monoester salt after the intensification, then, polyreaction 2.5h under 85 ℃ temperature, after reaction is finished, reaction product is cooled to 61 ℃, add deionized water then, the massfraction that makes water is 57% polymer retanning fat-liquoring agent.
Embodiment 6
1: 1.09 in molar ratio, get the pure and mild maleic anhydride of C12 long-chain fat respectively, the C12 long chain aliphatic alcohol is warming up to 73 ℃, add maleic anhydride, mix, then, be warming up to 92 ℃, insulation reaction 4h, synthetic C12 long chain aliphatic alcohol toxilic acid monoesters; Synthetic C12 long chain aliphatic alcohol toxilic acid monoesters is cooled to 63 ℃, add deionized water, the mass ratio of deionized water and C12 long chain aliphatic alcohol toxilic acid monoesters is 1.8: 1, stir 13min, then, with massfraction is that 30% potassium hydroxide aqueous solution splashes in 25～30min in the C12 long chain aliphatic alcohol toxilic acid monoesters that adds deionized water, makes that the pH value of the C12 long chain aliphatic alcohol toxilic acid monoesters that adds deionized water is 7.2, obtains C12 long chain aliphatic alcohol toxilic acid monoester salt; Pressed mass ratio 1.6: 1, fetch water respectively and methacrylic acid, the dilute with water methacrylic acid, then, with massfraction is in the methacrylic acid after 30% aqueous sodium hydroxide solution adds dilution, make the pH value and be 6.8 methacrylic acid sodium water solution, Sodium Persulfate, Potassium Persulphate and the ammonium persulphate of arbitrary proportion is dissolved in the water, make the initiator solution of mass concentration 25%; Get the methacrylic acid stearyl respectively, the C12 long chain aliphatic alcohol toxilic acid monoester salt that makes, methacrylic acid sodium water solution and initiator solution, the control initiator radical is 5% in the massfraction of comonomer total mass, in the C12 long chain aliphatic alcohol toxilic acid monoester salt in C12 long chain aliphatic alcohol toxilic acid monoesters and the methacrylic aqueous acid mol ratio of methacrylic acid be 1: 2.5, the mol ratio of C12 long chain aliphatic alcohol toxilic acid monoesters and methacrylic acid stearyl is 1: 0.8 in the C12 long chain aliphatic alcohol toxilic acid monoester salt, C12 long chain aliphatic alcohol toxilic acid monoester salt is warming up to 76 ℃, with the methacrylic acid stearyl, methacrylic acid sodium water solution and initiator solution splash into respectively in 1～3h in the C12 long chain aliphatic alcohol toxilic acid monoester salt after the intensification, then, polyreaction 1.75h under 76 ℃ temperature, after reaction is finished, reaction product is cooled to 63 ℃, add deionized water then, make the quality mark and be 59% polymer retanning fat-liquoring agent.
Embodiment 7
The 37.2g lauryl alcohol is added reactor, be warming up to 70 ℃, add the 20.58g maleic anhydride, after treating that maleic anhydride and lauryl alcohol mix, be warming up to 90 ℃, insulation reaction 2.5h, synthetic lauryl alcohol toxilic acid monoesters, synthetic lauryl alcohol toxilic acid monoesters is cooled to 60 ℃, adds the 20g deionized water, stir 10min, then, with the 29.33g massfraction is that 30% aqueous sodium hydroxide solution splashes in 25～30min in the lauryl alcohol toxilic acid monoesters that adds deionized water, and making the pH value of lauryl alcohol toxilic acid monoesters is 7.0, makes lauryl alcohol toxilic acid monoester salt.The 5.4g Sodium Persulfate is dissolved in the 21.6g deionized water, make initiator solution, with 17g water dilution 34.4g methacrylic acid, then, with the 53.33g massfraction is in the methacrylic acid after 30% aqueous sodium hydroxide solution adds dilution, makes the methacrylic acid sodium water solution.After lauryl alcohol toxilic acid monoester salt is warming up to 80 ℃, 27g initiator solution, 26.4g methacrylic acid stearyl and 104.73 methacrylic acid sodium water solutions are splashed in 1～3h in the lauryl alcohol toxilic acid monoester salt after the intensification, afterwards, continue insulation reaction 2h, reaction product is cooled to 60 ℃, add the 47.23g deionized water, transferring the massfraction of water in the reactant is 60%, makes methacrylic acid stearyl-long chain aliphatic alcohol toxilic acid monoesters-methacrylic acid ter-polymer composite tan fatting agent.
Embodiment 8
The 37.2g lauryl alcohol is added reactor, be warming up to 70 ℃, add the 20.58g maleic anhydride, after treating that maleic anhydride and lauryl alcohol mix, be warming up to 90 ℃, insulation reaction 2.5h, synthetic lauryl alcohol toxilic acid monoesters, synthetic lauryl alcohol toxilic acid monoesters is cooled to 60 ℃, adds the 20g deionized water, stir 10min, then, with the 29.33g massfraction is that 30% aqueous sodium hydroxide solution splashes in 25～30min in the lauryl alcohol toxilic acid monoesters that adds deionized water, and making the pH value of lauryl alcohol toxilic acid monoesters is 7.0, makes lauryl alcohol toxilic acid monoester salt.The 3.6g Sodium Persulfate is dissolved in the 14.4g deionized water, makes initiator solution.With 15g water dilution 25.8g methacrylic acid, then, be in the methacrylic acid after 30% aqueous sodium hydroxide solution adds dilution with the 40g massfraction, make the methacrylic acid sodium water solution.Lauryl alcohol toxilic acid monoester salt is warming up to 80 ℃, 18g initiator solution, 13.2g methacrylic acid stearyl and 80.8 methacrylic acid sodium water solutions are splashed in 1～3h in the lauryl alcohol toxilic acid monoester salt after the intensification, afterwards, continue insulation reaction 2h, reaction product is cooled to 60 ℃, add the 47.23g deionized water, transfer the massfraction 60% of reactants water, promptly get methacrylic acid stearyl-long chain aliphatic alcohol toxilic acid monoesters-methacrylic acid ter-polymer composite tan fatting agent.
Claims (10)
1. the preparation method of a polymer retanning fat-liquoring agent, adopt long chain aliphatic alcohol toxilic acid monoesters, methacrylic acid stearyl and methacrylic acid to carry out the water miscible liquid copolymerization and prepare polymer retanning fat-liquoring agent, it is characterized in that this preparation method carries out according to the following steps:
Step 1: 1: 1.05 in molar ratio～1.1, get the pure and mild maleic anhydride of long-chain fat respectively, long chain aliphatic alcohol is warming up to 70 ℃～75 ℃, add maleic anhydride, mix, then, be warming up to 90 ℃～110 ℃, insulation reaction 2h～5h, synthetic long chain aliphatic alcohol toxilic acid monoesters;
Step 2: synthetic long chain aliphatic alcohol toxilic acid monoesters in the step 1 is cooled to 60 ℃～65 ℃, add deionized water, the mass ratio of deionized water and long chain aliphatic alcohol toxilic acid monoesters is 1～2: 1, stir 10min～20min, then, basic cpd is splashed in 25min～30min in the long chain aliphatic alcohol toxilic acid monoesters that adds deionized water, and the feasible pH value that adds the long chain aliphatic alcohol toxilic acid monoesters of deionized water is 7.0～7.5, obtains long chain aliphatic alcohol toxilic acid monoester salt;
Step 3: press mass ratio 1～2: 1, fetch water and methacrylic acid the dilute with water methacrylic acid respectively, then, with massfraction is in the methacrylic acid after 30% aqueous sodium hydroxide solution adds dilution, makes the pH value and be 6.5～7.0 methacrylic acid sodium water solution
Get initiator, this initiator is dissolved in the water, make the initiator solution of mass concentration 20～30%;
Step 4: get the methacrylic acid stearyl respectively, the long chain aliphatic alcohol toxilic acid monoester salt that step 2 makes, methacrylic acid sodium water solution and initiator solution that step 3 makes, the control initiator radical is 2%～10% in the massfraction of comonomer total mass, in the long chain aliphatic alcohol toxilic acid monoester salt in long chain aliphatic alcohol toxilic acid monoesters and the methacrylic aqueous acid mol ratio of methacrylic acid be 1: 1～3, the mol ratio of long chain aliphatic alcohol toxilic acid monoesters and methacrylic acid stearyl is 1: 0.2～1.0 in the long chain aliphatic alcohol toxilic acid monoester salt, long chain aliphatic alcohol toxilic acid monoester salt is warming up to 75 ℃～90 ℃, with the methacrylic acid stearyl, methacrylic acid sodium water solution and initiator solution splash into respectively in 1h～3h in the long chain aliphatic alcohol toxilic acid monoester salt after the intensification, then, under 75 ℃～90 ℃ temperature, react 1.5h～3h, after reaction is finished, reaction product is cooled to 60～65 ℃, add deionized water then, make polymer retanning fat-liquoring agent.
2. according to the described preparation method of claim 1, it is characterized in that this preparation method carries out according to the following steps:
Step 1: 1: 1.05 in molar ratio～1.1, get C8～pure and mild maleic anhydride of C18 long-chain fat respectively, this long chain aliphatic alcohol is warming up to 70 ℃～75 ℃, add maleic anhydride, mix, then, be warming up to 90 ℃～110 ℃, insulation reaction 2h～5h, synthetic long chain aliphatic alcohol toxilic acid monoesters;
Step 2: synthetic long chain aliphatic alcohol toxilic acid monoesters in the step 1 is cooled to 60 ℃～65 ℃, add deionized water, the mass ratio of deionized water and long chain aliphatic alcohol toxilic acid monoesters is 1～2: 1, stir 10min～20min, then, basic cpd is splashed in 25min～30min in the long chain aliphatic alcohol toxilic acid monoesters that adds deionized water, and the feasible pH value that adds the long chain aliphatic alcohol toxilic acid monoesters of deionized water is 7.0～7.5, obtains long chain aliphatic alcohol toxilic acid monoester salt;
Step 3: press mass ratio 1～2: 1, fetch water and methacrylic acid the dilute with water methacrylic acid respectively, then, with massfraction is in the methacrylic acid after 30% aqueous sodium hydroxide solution adds dilution, makes the pH value and be 6.5～7.0 methacrylic acid sodium water solution
Step 4: get the methacrylic acid stearyl respectively, the long chain aliphatic alcohol toxilic acid monoester salt that step 2 makes, methacrylic acid sodium water solution and initiator solution that step 3 makes, the control initiator radical is 5～8% in the massfraction of comonomer total mass, in the long chain aliphatic alcohol toxilic acid monoester salt in long chain aliphatic alcohol toxilic acid monoesters and the methacrylic aqueous acid mol ratio of methacrylic acid be 1: 1.5～2.0, the mol ratio of long chain aliphatic alcohol toxilic acid monoesters and methacrylic acid stearyl is 1: 0.4～0.6 in the long chain aliphatic alcohol toxilic acid monoester salt, long chain aliphatic alcohol toxilic acid monoester salt is warming up to 75 ℃～90 ℃, with the methacrylic acid stearyl, methacrylic aqueous acid and initiator solution splash into respectively in 1h～3h in the long chain aliphatic alcohol toxilic acid monoester salt after the intensification, then, under 80 ℃～85 ℃ temperature, react 2.0h～2.5h, after reaction is finished, reaction product is cooled to 60～65 ℃, add deionized water then, make polymer retanning fat-liquoring agent.
3. according to claim 1 or 2 described preparation methods, it is characterized in that the long chain aliphatic alcohol in the described step 1 is C8～C18 long chain aliphatic alcohol.
4. according to claim 1 or 2 described preparation methods, it is characterized in that it is that 30% aqueous sodium hydroxide solution or massfraction are 30% potassium hydroxide aqueous solution that basic cpd in the described step 2 adopts ammoniacal liquor, massfraction.
5. according to claim 1 or 2 described preparation methods, it is characterized in that, initiator in the described step 3 adopts a kind of in Sodium Persulfate, Potassium Persulphate or the ammonium persulphate, perhaps two kinds combination, perhaps three kinds combination, when adopting two kinds of combinations or three kinds of combinations, between the each component arbitrary proportion.
6. according to claim 1 or 2 described preparation methods, it is characterized in that the massfraction of water is 55～60% in the described polymer retanning fat-liquoring agent that makes.
7. a polymer retanning fat-liquoring agent that utilizes the described preparation method of claim 1 to make is characterized in that, this composite tan fatting agent adopts following method to prepare:
Step 1: 1: 1.05 in molar ratio～1.1, get C8～pure and mild maleic anhydride of C18 long-chain fat respectively, this long chain aliphatic alcohol is warming up to 70 ℃～75 ℃, add maleic anhydride, mix, then, be warming up to 90 ℃～110 ℃, insulation reaction 2h～5h, synthetic long chain aliphatic alcohol toxilic acid monoesters;
Step 2: synthetic long chain aliphatic alcohol toxilic acid monoesters in the step 1 is cooled to 60 ℃～65 ℃, add deionized water, the mass ratio of deionized water and long chain aliphatic alcohol toxilic acid monoesters is 1～2: 1, stir 10min～20min, then, basic cpd is splashed in 25min～30min in the long chain aliphatic alcohol toxilic acid monoesters that adds deionized water, and the feasible pH value that adds the long chain aliphatic alcohol toxilic acid monoesters of deionized water is 7.0～7.5, obtains long chain aliphatic alcohol toxilic acid monoester salt;
Step 3: press mass ratio 1～2: 1, fetch water and methacrylic acid the dilute with water methacrylic acid respectively, then, with massfraction is in the methacrylic acid after 30% aqueous sodium hydroxide solution adds dilution, makes the pH value and be 6.5～7.0 methacrylic acid sodium water solution
Get initiator, this initiator is dissolved in the water, make the initiator solution of mass concentration 20～30%;
Step 4: get the methacrylic acid stearyl respectively, the long chain aliphatic alcohol toxilic acid monoester salt that step 2 makes, methacrylic acid sodium water solution and initiator solution that step 3 makes, the control initiator radical is 2%～10% in the massfraction of comonomer total mass, in the long chain aliphatic alcohol toxilic acid monoester salt in long chain aliphatic alcohol toxilic acid monoesters and the methacrylic aqueous acid mol ratio of methacrylic acid be 1: 1～3, the mol ratio of long chain aliphatic alcohol toxilic acid monoesters and methacrylic acid stearyl is 1: 0.2～1.0 in the long chain aliphatic alcohol toxilic acid monoester salt, long chain aliphatic alcohol toxilic acid monoester salt is warming up to 75 ℃～90 ℃, with the methacrylic acid stearyl, methacrylic aqueous acid and initiator solution splash into respectively in 1h～3h in the long chain aliphatic alcohol toxilic acid monoester salt after the intensification, then, under 75 ℃～90 ℃ temperature, react 1.5h～3h, after reaction is finished, reaction product is cooled to 60～65 ℃, add deionized water then, make polymer retanning fat-liquoring agent, comprise methacrylic acid stearyl-long chain aliphatic alcohol toxilic acid monoesters-methacrylic acid ter-polymer in this composite tan fatting agent.
8. according to the described composite tan fatting agent of claim 7, it is characterized in that it is that 30% aqueous sodium hydroxide solution or massfraction are 30% potassium hydroxide aqueous solution that basic cpd in the described step 2 adopts ammoniacal liquor, massfraction.
9. according to the described composite tan fatting agent of claim 7, it is characterized in that, initiator in the described step 3 adopts a kind of in Sodium Persulfate, Potassium Persulphate or the ammonium persulphate, perhaps two kinds combination, perhaps three kinds combination, when adopting two kinds of combinations or three kinds of combinations, between the each component arbitrary proportion.
10. according to the described composite tan fatting agent of claim 7, it is characterized in that the massfraction of water is 55～60% in the polymer retanning fat-liquoring agent that makes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010175187 CN101831024A (en) | 2010-05-15 | 2010-05-15 | Method for preparing polymer retanning fat-liquoring agent and retanning fat-liquoring agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010175187 CN101831024A (en) | 2010-05-15 | 2010-05-15 | Method for preparing polymer retanning fat-liquoring agent and retanning fat-liquoring agent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101831024A true CN101831024A (en) | 2010-09-15 |
Family
ID=42715258
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010175187 Pending CN101831024A (en) | 2010-05-15 | 2010-05-15 | Method for preparing polymer retanning fat-liquoring agent and retanning fat-liquoring agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101831024A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102757528A (en) * | 2012-06-21 | 2012-10-31 | 陕西科技大学 | Preparation method of amphoteric retanning fatliquor |
| CN103131804A (en) * | 2013-02-02 | 2013-06-05 | 四川德赛尔化工实业有限公司 | Amphiprotic amphiphilic leather retanning fatting agent and preparation method thereof |
| CN104804120A (en) * | 2015-05-12 | 2015-07-29 | 四川德赛尔化工实业有限公司 | Preparation method for polymer fat-liquoring agent containing sulfosuccinate salt structure |
| CN111979365A (en) * | 2020-08-19 | 2020-11-24 | 扬州工业职业技术学院 | Soybean lecithin retanning fatting agent with mildew-proof performance and preparation method thereof |
| CN112679650A (en) * | 2020-12-23 | 2021-04-20 | 齐河力厚化工有限公司 | Amphoteric synthetic fat liquor, preparation method and application thereof |
| CN113372475A (en) * | 2021-06-24 | 2021-09-10 | 齐鲁工业大学 | Method for preparing waterproof polymer fatliquor |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070107135A1 (en) * | 2003-07-23 | 2007-05-17 | Basf Aktiengesellschaft | Method for the production of leather by using polymers |
-
2010
- 2010-05-15 CN CN 201010175187 patent/CN101831024A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070107135A1 (en) * | 2003-07-23 | 2007-05-17 | Basf Aktiengesellschaft | Method for the production of leather by using polymers |
Non-Patent Citations (2)
| Title |
|---|
| 《石油化工》 20081215 邹祥龙等 十二烷基正丁基琥珀酸混合双酯磺酸钠的合成 第1306-1310页 第37卷, 第12期 2 * |
| 《石油化工》 20091215 邹祥龙等 马来酸单酯-甲基丙烯酸酯-甲基丙烯酸三元共聚物复鞣加脂剂的制备及其性能 第1327-1330页 第38卷, 第12期 2 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102757528A (en) * | 2012-06-21 | 2012-10-31 | 陕西科技大学 | Preparation method of amphoteric retanning fatliquor |
| CN102757528B (en) * | 2012-06-21 | 2014-02-05 | 陕西科技大学 | Preparation method of amphoteric retanning fatliquor |
| CN103131804A (en) * | 2013-02-02 | 2013-06-05 | 四川德赛尔化工实业有限公司 | Amphiprotic amphiphilic leather retanning fatting agent and preparation method thereof |
| CN103131804B (en) * | 2013-02-02 | 2014-03-26 | 四川德赛尔化工实业有限公司 | Amphiprotic amphiphilic leather retanning fatting agent and preparation method thereof |
| CN104804120A (en) * | 2015-05-12 | 2015-07-29 | 四川德赛尔化工实业有限公司 | Preparation method for polymer fat-liquoring agent containing sulfosuccinate salt structure |
| CN104804120B (en) * | 2015-05-12 | 2017-11-07 | 四川德赛尔化工实业有限公司 | A kind of preparation method of the polymer fatliquoring agent containing sulfosuccinates salt structure |
| CN111979365A (en) * | 2020-08-19 | 2020-11-24 | 扬州工业职业技术学院 | Soybean lecithin retanning fatting agent with mildew-proof performance and preparation method thereof |
| CN111979365B (en) * | 2020-08-19 | 2022-06-14 | 扬州工业职业技术学院 | Soybean lecithin retanning fatting agent with mildew-proof performance and preparation method thereof |
| CN112679650A (en) * | 2020-12-23 | 2021-04-20 | 齐河力厚化工有限公司 | Amphoteric synthetic fat liquor, preparation method and application thereof |
| CN113372475A (en) * | 2021-06-24 | 2021-09-10 | 齐鲁工业大学 | Method for preparing waterproof polymer fatliquor |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101831024A (en) | Method for preparing polymer retanning fat-liquoring agent and retanning fat-liquoring agent | |
| CN101974135B (en) | Normal-temperature synthesis method for polycarboxylic acid water-reducing agent | |
| CN102757528B (en) | Preparation method of amphoteric retanning fatliquor | |
| CN101760570B (en) | Composite leather greasing agent and preparation method thereof | |
| CN105254792B (en) | A kind of modified Cardanol derivative water reducer and preparation method thereof | |
| CN103131804B (en) | Amphiprotic amphiphilic leather retanning fatting agent and preparation method thereof | |
| CN109575198A (en) | A kind of reinforcing type polycarboxylic acid water-reducing agent and preparation method thereof | |
| CN102154852A (en) | Textile machinery printing pigment binding agent and manufacturing method thereof | |
| CN104804120A (en) | Preparation method for polymer fat-liquoring agent containing sulfosuccinate salt structure | |
| CN101323886A (en) | Preparation of acrylic polymer retanning agent for highly elastic leather retanning | |
| DE4242039A1 (en) | Copolymers and their use for the treatment of leather | |
| CN103073459A (en) | Preparation method for laurinol polyoxyethylene ether (7) isooctyl sulfosuccinate mixed sodium diester | |
| CN102001975A (en) | Ethylene glycol bi-sulpho succinic acid bi(2-methyl amyl) artesunate and production method thereof | |
| CN104313205A (en) | Succinate sulfonated C16-C18 alcohol surfactant and preparation method thereof | |
| CN105949369B (en) | The preparation method of leather multifunctional water talcum/polymer nanocomposite composite assistant | |
| CN1026590C (en) | Making method of multi-functional acrylic acid double tanning agent | |
| CN101457262B (en) | Method for preparing leather retanning fat-liquoring agent | |
| CN102702659B (en) | Method for preparing multifunctional retanning agents through modified starch and MMT in compounding mode | |
| CN101914874B (en) | Colophony-containing surface sizing agent, preparation method and application thereof | |
| CN106544453A (en) | Both sexes composite tan fatting agent and preparation method thereof | |
| CN104561400B (en) | Sulfonated leather greasing agent containing fatty acid low-carbon ester and preparation method thereof | |
| CN102120797B (en) | Preparation method of sulfonated styrene-styrene-maleic acid fatty alcohol monoester sodium salt terpolymer tanning agent | |
| CN102153699A (en) | Method for preparing leather retanning and greasing agent of poly (long-chain fatty alcohol-itaconic acid monoester) and acrylic acid copolymer | |
| CN111394191A (en) | Preparation method of oil-based sulfosuccinic acid monoester type amphoteric fatliquor | |
| CN102199244B (en) | Phosphate leather retanning fatliquoring agent and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20100915 |