CN101603102B - Preparation method of composite water-proof leather fat-liquoring agent - Google Patents
Preparation method of composite water-proof leather fat-liquoring agent Download PDFInfo
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- CN101603102B CN101603102B CN2009100231429A CN200910023142A CN101603102B CN 101603102 B CN101603102 B CN 101603102B CN 2009100231429 A CN2009100231429 A CN 2009100231429A CN 200910023142 A CN200910023142 A CN 200910023142A CN 101603102 B CN101603102 B CN 101603102B
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Abstract
The invention provides a preparation method of composite water-proof leather fat-liquoring agent. The composite water-proof leather fat-liquoring agent contains sulfonation succinic acid tallow primary amine, fatty alcohol organic phosphate and neutral oil, wherein, the tallow primary amine is modified with maleic anhydride to obtain succinic acid tallow primary amine containing amido bond; then, the succinic acid tallow primary amine is sulfonated to obtain sulfonation succinic acid tallow primary amine; the fatty alcohol organic phosphate and the neutral oil are led into the sulfonation succinic acid tallow primary amine so as to obtain the composite water-proof leather via neutralization and adjusting effective substance contents. The product of the invention is white, and has high storing stability; after treated by the fat-liquoring agent of the invention, the tensile strength, lubrication feeling, plumpness, flexibility and elasticity of the leather are improved, and the water-proof performance of the leather is obviously improved.
Description
Technical field
The present invention relates to a kind of preparation method of leather fat, particularly a kind of preparation method of composite water-proof leather fat-liquoring agent.
Background technology
Fatting agent is the maximum skin material of consumption in the tanning production, also is one of important chemical materials in the leather processing procedure.It can lubricate leather fiber, prevents stiff, the cracking of leather, can make leather have corresponding toughness and flexibility again, and keep its intensity, and it is the important factor that influences the leather quality performance.The Along with people's growth in the living standard, the human consumer has higher requirement to leatherware, requires leatherware that the style of fashion should be arranged, and having to have unique feel, also should possess waterproof, performance such as washable, to improve the practicality and the wearing quality of leatherware.Therefore whippy feel and certain water resistance in order to give the plentiful softness of leather, this just need adopt the fatting agent stuffing with good waterproof action when stuffing.
At present, domestic preparation have waterproof action fatting agent the method that generally adopts be with vinylformic acid high-carbon alcohol ester and methylacrylic acid copolymerization, perhaps higher alcohols and Vanadium Pentoxide in FLAKES to be reacted the generation alkyl phosphate, or organosilicon is carried out modification.Though there is certain waterproof stuffing function in the waterproof currying agent of these types,, have that glossy property is strong, feel is owed shortcomings such as sliding wax because it is one-component.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of composite water-proof leather fat-liquoring agent, not only have tangible waterproof effect with the composite water-proof fatting agent of this method preparation, and also fine through glossy sense, fullness ratio, the pliability of the leather of its effect.
For achieving the above object, the present invention has adopted following technical scheme:
1) preparation of sulfosuccinate butter primary amine: at first with butter primary amine and organic solvent according to 1: 0～1: 2 mass ratio mix mixture; Be warming up to 40～100 ℃ again by the butter primary amine: maleic anhydride is to react 2～6 hours down at 80～150 ℃ 1: 0.9～1: 1.1 mass ratio adds maleic anhydride in mixture after; Accomplish the back by maleic anhydride Deng reaction: sulfonated reagent is that 1: 0.9～1: 1.1 mass ratio adds sulfonated reagent in the reaction system to, and controlled temperature is 60～100 ℃ and reacts 1～4h and get sulfosuccinate butter primary amine;
2) preparation of fatty alcohol phosphate: under 40～100 ℃, in Fatty Alcohol(C12-C14 and C12-C18), slowly add phosphorylation agent, wherein the mass ratio of Fatty Alcohol(C12-C14 and C12-C18) and phosphorylation agent is 1: 0.4～1: 0.5, reacts 2～6 hours down at 70～120 ℃; 8%～20% of interpolation phosphorylation agent quality water in reaction system continues reaction down at 70～120 ℃ and got fatty alcohol phosphate in 1～4 hour then;
3) composite: that the sulfosuccinate butter primary amine of step 1) is cooled to 50～60 ℃ to wherein adding step 2) in fatty alcohol phosphate and neutral oil mix at 40～70 ℃; Contain 20%～40% sulfosuccinate butter primary amine in the said mixture by mass fraction, 20%～40% fatty alcohol phosphate and 20%～40% neutral oil; Use sodium hydroxide to regulate the pH value then and be 6.5-7.5, in system, adding entry adjusting working substance content again is 40%～60%, continues to stir 0.5～2h, promptly obtains the final product composite water-proof leather fat-liquoring agent.
Organic solvent described in the present invention is N, dinethylformamide, diethylene glycol dimethyl ether or ethylene glycol dibutyl ether; Said sulfonated reagent is a Sodium Pyrosulfite; Said Fatty Alcohol(C12-C14 and C12-C18) is lauryl alcohol, tetradecyl alcohol, hexadecanol, stearyl alcohol, C
12～14Alcohol mixture or C
16～18Alcohol mixture; Said phosphorylation agent is a Vanadium Pentoxide in FLAKES; Said neutral oil is natural neat's foot oil, No. 10 white oils or rape oil fatty acid methyl esters.
Because the present invention is composite with several kinds of different water-repellancy fatting agent and neutral oils, has good self-emulsifying ability, the water-repellancy fatting agent of gained good emulsion stability thereby neutralize to make with alkali then.After with it leather being handled, the water resistance of leather obviously strengthens, and tensile strength, glossy sense, fullness ratio, pliability, the elasticity of leather all improve significantly.
Embodiment
The present invention has adopted three-step approach to prepare leather fat, i.e. the mixing of the preparation of the preparation of sulfosuccinate butter primary amine, fatty alcohol phosphate, sulfosuccinate butter primary amine and fatty alcohol phosphate and adding neutral oil are re-dubbed leather fat.
Embodiment 1:
1) preparation of sulfosuccinate butter primary amine: at first the butter primary amine is warming up to 80 ℃ again by the butter primary amine: maleic anhydride is to react 4 hours down at 100 ℃ after 1: 0.9 mass ratio adds maleic anhydride; Accomplish the back by maleic anhydride Deng reaction: Sodium Pyrosulfite is that 1: 1.1 mass ratio adds Sodium Pyrosulfite in the reaction system to, and controlled temperature is 80 ℃ and reacts 2h and get sulfosuccinate butter primary amine;
2) preparation of fatty alcohol phosphate: under 80 ℃, in lauryl alcohol, slowly add Vanadium Pentoxide in FLAKES, wherein the mass ratio of lauryl alcohol and Vanadium Pentoxide in FLAKES is 1: 0.4, reacts 4 hours down at 100 ℃; 15% of interpolation Vanadium Pentoxide in FLAKES quality water in reaction system continues reaction down at 100 ℃ and got fatty alcohol phosphate in 3 hours then;
3) composite: that the sulfosuccinate butter primary amine of step 1) is cooled to 60 ℃ to wherein adding step 2) in fatty alcohol phosphate and natural neat's foot oil mix at 60 ℃; Contain 20% sulfosuccinate butter primary amine in the said mixture by mass fraction, 40% fatty alcohol phosphate and 40% natural neat's foot oil; Using sodium hydroxide to regulate the pH value then is 6.5, and in system, adding entry adjusting working substance content again is 40%, continues to stir 0.5h, promptly obtains the final product composite water-proof leather fat-liquoring agent.
Embodiment 2:
1) preparation of sulfosuccinate butter primary amine: at first with butter primary amine and organic solvent N; Dinethylformamide according to 1: 0.5 mass ratio mix mixture; Be warming up to 40 ℃ again by the butter primary amine: maleic anhydride is to react 2 hours down at 150 ℃ 1: 1.0 mass ratio adds maleic anhydride in mixture after; Accomplish the back by maleic anhydride Deng reaction: Sodium Pyrosulfite is that 1: 0.9 mass ratio adds Sodium Pyrosulfite in the reaction system to, and controlled temperature is 60 ℃ and reacts 4h and get sulfosuccinate butter primary amine;
2) preparation of fatty alcohol phosphate: under 60 ℃, in tetradecyl alcohol, slowly add Vanadium Pentoxide in FLAKES, wherein the mass ratio of tetradecyl alcohol and Vanadium Pentoxide in FLAKES is 1: 0.5, reacts 6 hours down at 70 ℃; 8% of interpolation Vanadium Pentoxide in FLAKES quality water in reaction system continues reaction down at 70 ℃ and got fatty alcohol phosphate in 4 hours then;
3) composite: that the sulfosuccinate butter primary amine of step 1) is cooled to 58 ℃ to wherein adding step 2) in fatty alcohol phosphate and No. 10 white oils mix at 50 ℃; Contain 30% sulfosuccinate butter primary amine in the said mixture by mass fraction, 35% fatty alcohol phosphate and 35% No. 10 white oils; Using sodium hydroxide to regulate the pH value then is 7, and in system, adding entry adjusting working substance content again is 50%, continues to stir 1h, promptly obtains the final product composite water-proof leather fat-liquoring agent.
Embodiment 3:
1) preparation of sulfosuccinate butter primary amine: at first with butter primary amine and organic solvent diethylene glycol dimethyl ether according to 1: 2 mass ratio mix mixture; Be warming up to 100 ℃ again by the butter primary amine: maleic anhydride is to react 6 hours down at 80 ℃ 1: 1.1 mass ratio adds maleic anhydride in mixture after; Accomplish the back by maleic anhydride Deng reaction: Sodium Pyrosulfite is that 1: 1.0 mass ratio adds Sodium Pyrosulfite in the reaction system to, and controlled temperature is 100 ℃ and reacts 1h and get sulfosuccinate butter primary amine;
2) preparation of fatty alcohol phosphate: under 100 ℃, in hexadecanol, slowly add Vanadium Pentoxide in FLAKES, wherein the mass ratio of hexadecanol and Vanadium Pentoxide in FLAKES is 1: 0.45, reacts 4.5 hours down at 90 ℃; 17% of interpolation Vanadium Pentoxide in FLAKES quality water in reaction system continues reaction down at 90 ℃ and got fatty alcohol phosphate in 2 hours then;
3) composite: that the sulfosuccinate butter primary amine of step 1) is cooled to 55 ℃ to wherein adding step 2) in fatty alcohol phosphate and rape oil fatty acid methyl esters mix at 70 ℃; Contain 40% sulfosuccinate butter primary amine in the said mixture by mass fraction, 20% fatty alcohol phosphate and 40% rape oil fatty acid methyl esters; Using sodium hydroxide to regulate the pH value then is 7.5, and in system, adding entry adjusting working substance content again is 60%, continues to stir 2h, promptly obtains the final product composite water-proof leather fat-liquoring agent.
Embodiment 4:
1) preparation of sulfosuccinate butter primary amine: at first with butter primary amine and organic solvent ethylene glycol dibutyl ether according to 1: 1.2 mass ratio mix mixture; Be warming up to 60 ℃ again by the butter primary amine: maleic anhydride is to react 3 hours down at 120 ℃ 1: 1.0 mass ratio adds maleic anhydride in mixture after; Accomplish the back by maleic anhydride Deng reaction: Sodium Pyrosulfite is that 1: 0.9 mass ratio adds Sodium Pyrosulfite in the reaction system to, and controlled temperature is 70 ℃ and reacts 2.5h and get sulfosuccinate butter primary amine;
2) preparation of fatty alcohol phosphate: under 70 ℃, in stearyl alcohol, slowly add Vanadium Pentoxide in FLAKES, wherein the mass ratio of stearyl alcohol and Vanadium Pentoxide in FLAKES is 1: 0.48, reacts 2 hours down at 120 ℃; 10% of interpolation Vanadium Pentoxide in FLAKES quality water in reaction system continues reaction down at 120 ℃ and got fatty alcohol phosphate in 1 hour then;
3) composite: that the sulfosuccinate butter primary amine of step 1) is cooled to 53 ℃ to wherein adding step 2) in fatty alcohol phosphate and natural neat's foot oil mix at 40 ℃; Contain 40% sulfosuccinate butter primary amine in the said mixture by mass fraction, 40% fatty alcohol phosphate and 20% natural neat's foot oil; Using sodium hydroxide to regulate the pH value then is 6.8, and in system, adding entry adjusting working substance content again is 45%, continues to stir 1.5h, promptly obtains the final product composite water-proof leather fat-liquoring agent.
Embodiment 5:
1) preparation of sulfosuccinate butter primary amine: at first with butter primary amine and organic solvent N; Dinethylformamide according to 1: 1.8 mass ratio mix mixture; Be warming up to 90 ℃ again by the butter primary amine: maleic anhydride is to react 5 hours down at 90 ℃ 1: 1.1 mass ratio adds maleic anhydride in mixture after; Accomplish the back by maleic anhydride Deng reaction: Sodium Pyrosulfite is that 1: 1.0 mass ratio adds Sodium Pyrosulfite in the reaction system to, and controlled temperature is 90 ℃ and reacts 1.5h and get sulfosuccinate butter primary amine;
2) preparation of fatty alcohol phosphate: under 40 ℃ to C
12～14Slowly add Vanadium Pentoxide in FLAKES, wherein C in the alcohol mixture
12～14The mass ratio of alcohol mixture and Vanadium Pentoxide in FLAKES is 1: 0.43, reacts 5 hours down at 80 ℃; 13% of interpolation Vanadium Pentoxide in FLAKES quality water in reaction system continues reaction down at 80 ℃ and got fatty alcohol phosphate in 2.5 hours then;
3) composite: that the sulfosuccinate butter primary amine of step 1) is cooled to 50 ℃ to wherein adding step 2) in fatty alcohol phosphate and No. 10 white oils mix at 55 ℃; Contain 32% sulfosuccinate butter primary amine in the said mixture by mass fraction, 38% fatty alcohol phosphate and 30% No. 10 white oils; Using sodium hydroxide to regulate the pH value then is 7.2, and in system, adding entry adjusting working substance content again is 55%, continues to stir 1h, promptly obtains the final product composite water-proof leather fat-liquoring agent.
Embodiment 6:
1) preparation of sulfosuccinate butter primary amine: at first with butter primary amine and organic solvent ethylene glycol dibutyl ether according to 1: 1.5 mass ratio mix mixture; Be warming up to 70 ℃ again by the butter primary amine: maleic anhydride is to react 2.5 hours down at 140 ℃ 1: 0.9 mass ratio adds maleic anhydride in mixture after; Accomplish the back by maleic anhydride Deng reaction: Sodium Pyrosulfite is that 1: 1.1 mass ratio adds Sodium Pyrosulfite in the reaction system to, and controlled temperature is 85 ℃ and reacts 3h and get sulfosuccinate butter primary amine;
2) preparation of fatty alcohol phosphate: under 90 ℃ to C
16～18Slowly add Vanadium Pentoxide in FLAKES, wherein C in the alcohol mixture
16～18The mass ratio of alcohol mixture and Vanadium Pentoxide in FLAKES is 1: 0.5, reacts 3 hours down at 110 ℃; 20% of interpolation Vanadium Pentoxide in FLAKES quality water in reaction system continues reaction down at 110 ℃ and got fatty alcohol phosphate in 1.5 hours then;
3) composite: that the sulfosuccinate butter primary amine of step 1) is cooled to 52 ℃ to wherein adding step 2) in fatty alcohol phosphate and rape oil fatty acid methyl esters mix at 65 ℃; Contain 38% sulfosuccinate butter primary amine in the said mixture by mass fraction, 30% fatty alcohol phosphate and 32% rape oil fatty acid methyl esters; Using sodium hydroxide to regulate the pH value then is 7, and in system, adding entry adjusting working substance content again is 48%, continues to stir 2h, promptly obtains the final product composite water-proof leather fat-liquoring agent.
Claims (5)
1. the preparation method of a composite water-proof leather fat-liquoring agent is characterized in that:
1) preparation of sulfosuccinate butter primary amine: at first with butter primary amine and organic solvent according to 1: 0～1: 2 mass ratio mix mixture; Be warming up to 40～100 ℃ again by the butter primary amine: maleic anhydride is to react 2～6 hours down at 80～150 ℃ 1: 0.9～1: 1.1 mass ratio adds maleic anhydride in mixture after; Accomplish the back by maleic anhydride Deng reaction: sulfonated reagent is that 1: 0.9～1: 1.1 mass ratio adds sulfonated reagent in the reaction system to, and controlled temperature is 60～100 ℃ and reacts 1～4h and get sulfosuccinate butter primary amine;
2) preparation of fatty alcohol phosphate: under 40～100 ℃, in Fatty Alcohol(C12-C14 and C12-C18), slowly add Vanadium Pentoxide in FLAKES, wherein the mass ratio of Fatty Alcohol(C12-C14 and C12-C18) and Vanadium Pentoxide in FLAKES is 1: 0.4～1: 0.5, reacts 2～6 hours down at 70～120 ℃; 8%～20% of interpolation Vanadium Pentoxide in FLAKES quality water in reaction system continues reaction down at 70～120 ℃ and got fatty alcohol phosphate in 1～4 hour then;
3) composite: that the sulfosuccinate butter primary amine of step 1) is cooled to 50～60 ℃ to wherein adding step 2) in fatty alcohol phosphate and neutral oil mix at 40～70 ℃; Contain 20%～40% sulfosuccinate butter primary amine in the said mixture by mass fraction, 20%～40% fatty alcohol phosphate and 20%～40% neutral oil; Use sodium hydroxide to regulate the pH value then and be 6.5-7.5, in system, adding entry adjusting working substance content again is 40%～60%, continues to stir 0.5～2h, promptly obtains the final product composite water-proof leather fat-liquoring agent.
2. the preparation method of composite water-proof leather fat-liquoring agent according to claim 1, it is characterized in that: said organic solvent is N, dinethylformamide, diethylene glycol dimethyl ether or ethylene glycol dibutyl ether.
3. the preparation method of composite water-proof leather fat-liquoring agent according to claim 1, it is characterized in that: said sulfonated reagent is a Sodium Pyrosulfite.
4. the preparation method of composite water-proof leather fat-liquoring agent according to claim 1, it is characterized in that: said Fatty Alcohol(C12-C14 and C12-C18) is lauryl alcohol, tetradecyl alcohol, hexadecanol, stearyl alcohol, C
12～14Alcohol mixture or C
16～18Alcohol mixture.
5. the preparation method of composite water-proof leather fat-liquoring agent according to claim 1 is characterized in that: said neutral oil is natural neat's foot oil, No. 10 white oils or rape oil fatty acid methyl esters.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101760570B (en) * | 2009-12-29 | 2013-05-01 | 温州大学 | Composite leather greasing agent and preparation method thereof |
| CN103088169B (en) * | 2013-02-07 | 2014-10-22 | 浙江传化股份有限公司 | Leather comprehensive fat liquor and preparation method of the same |
| CN104651546A (en) * | 2013-11-21 | 2015-05-27 | 谈丽娜 | Composite-type phosphate leather fatliquor and preparation method thereof |
| CN106191343B (en) * | 2016-08-29 | 2018-07-17 | 上海金狮化工有限公司 | One kind kicking skin oil and preparation method thereof |
| CN106148591A (en) * | 2016-08-30 | 2016-11-23 | 四川达威科技股份有限公司 | A kind of waterproof currying agent and preparation method thereof |
| CN108265135B (en) * | 2018-02-07 | 2020-06-05 | 佛山市顺德区龙亭新材料有限公司 | Waterproof fatting agent and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2367301A (en) * | 2000-06-06 | 2002-04-03 | Rhodia Cons Spec Ltd | Tanning composition |
| CN1546690A (en) * | 2003-12-15 | 2004-11-17 | 陕西科技大学 | Lanolin leather fatting agent preparation method |
| CN1912146A (en) * | 2006-08-11 | 2007-02-14 | 温州大学 | Preparation method of sulphonating succinate ester disodium salt combined leather currying agent |
| CN101215612A (en) * | 2007-12-26 | 2008-07-09 | 宁波工程学院 | Method for preparing composite tan fatting agent from discarded phospholipid |
-
2009
- 2009-06-30 CN CN2009100231429A patent/CN101603102B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2367301A (en) * | 2000-06-06 | 2002-04-03 | Rhodia Cons Spec Ltd | Tanning composition |
| CN1546690A (en) * | 2003-12-15 | 2004-11-17 | 陕西科技大学 | Lanolin leather fatting agent preparation method |
| CN1912146A (en) * | 2006-08-11 | 2007-02-14 | 温州大学 | Preparation method of sulphonating succinate ester disodium salt combined leather currying agent |
| CN101215612A (en) * | 2007-12-26 | 2008-07-09 | 宁波工程学院 | Method for preparing composite tan fatting agent from discarded phospholipid |
Non-Patent Citations (1)
| Title |
|---|
| 廖银念，强西怀，周亚丽.皮革防水加脂剂的活性组分结构与其防水性相关性的研究.《陕西科技大学学报》.2006,第24卷(第2期),47-49. * |
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