CN1397650A - Process for preparing greasing-retanning agnt of leather - Google Patents
Process for preparing greasing-retanning agnt of leather Download PDFInfo
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- CN1397650A CN1397650A CN 01108632 CN01108632A CN1397650A CN 1397650 A CN1397650 A CN 1397650A CN 01108632 CN01108632 CN 01108632 CN 01108632 A CN01108632 A CN 01108632A CN 1397650 A CN1397650 A CN 1397650A
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- leather
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Abstract
A process for preparing the greasing-retanning agent of leather uses natural animal's fat and plant oil as raw amterial, and includes fat exchange, esterifying reaction, synthesizing oil prepolymer containing active dual bonds at terminal, and graft-copolymerizing-modifying reaction at 70-90 degC for 3-6 hrs, where sulfate is used as trigger and the Wt. ratio of oil to acrylic acid and its derivative is 1:(0.3-0.5). Its advantage is simple process.
Description
The invention belongs to the preparation field of leather chemical industry material, specifically is the preparation method of greasing-retanning agnt of leather.
Greasing-retanning agnt of leather has very unique effect in tanning production, it had both kept the premium properties of fatting agent, made the leather hand feeling softness glossy, had the characteristic of retanning agent again, gave leather goods with plentiful and elasticity.At present the lubricating retanning agent preparation method has two kinds: 1, long chain aliphatic alcohol and unsaturated acid lipoidization, be polymerized; (2) higher natural fats and oils and the vinyl monomer of iodine number is polymerized.Preceding kind method lubricating retanning agent stuffing weak effect, back kind method natural fats and oils and reactive vinyl monomer rate are low, the easy layering of finished product.
The objective of the invention is to overcome the defective of prior art, provide a kind of product performance good, finished product is difficult for layering, and manufacture craft is simple, the preparation method of the greasing-retanning agnt of leather that cost is low.
The objective of the invention is to realize by following technical proposals rice.
The preparation method of greasing-retanning agnt of leather of the present invention is:
(1) be basic material with natural animal-plant oil, by the fat exchange, esterification, synthetic end contains the grease performed polymer of activated double bonds;
(2) with the persulphate be initiator, carry out grafting, copolymerization and modification, make greasing-retanning agnt of leather by vinylformic acid and derivative thereof and above-mentioned performed polymer;
Above-mentioned natural animal-plant oil is 1: 0.3～0.5 with the weight ratio of vinylformic acid and derivative thereof, and modification by copolymerization is reflected in the aqueous solution carries out, PH=6～8, and temperature of reaction is 70～90 ℃, the time is 3～6 hours.
In the such scheme, described crude vegetal is siccative oil, semi-drying oil, nondrying oil, rape oil, Semen Lini oil, Chinese catalpa oil, soya-bean oil, Viscotrol C, lard etc.
In the such scheme, described fat exchange, esterifying reaction method is a prior art.
In the such scheme, described vinylformic acid and derivative thereof are one or more in vinylformic acid, methacrylic acid, the vinyl cyanide.Can also be CALCIUM ACRYLATE, methylol CALCIUM ACRYLATE etc.
In the such scheme, the add-on of described initiator is 0.8%～1.5% of a reaction-ure mixture, and initiator can also be a sodium bisulfite---the redox system of persulfuric acid sodium salt.
In the such scheme, the weight ratio of grease and vinylformic acid and derivative thereof is 1: 0.3～0.5, and grease amount is big, the lubricating retanning agent poorly water-soluble, and grease amount is few, good water solubility, but lubricating retanning agent viscosity is big, and the oil sense is poor.Modification by copolymerization is carried out in the aqueous solution, PH=6～8, and pH value is too low, is prone to precipitation in the reaction, and pH value is too high, grease performed polymer facile hydrolysis.
It is less to contain the response type group in the grease molecule, poor with the bonding force of chromium, can not keep finished product to remove from office soft persistence, and contain response type genes such as hydroxyl, carboxyl in vinylformic acid and the derivative molecular thereof, it and chrome tanned leather bonding force are strong, the leather softness after the stuffing retanning and high resilience.The objective of the invention is to want the premium properties of acrylic resin retanning agent is combined with greasy premium properties, make the multifunctional leather formed material that not only has the stuffing function but also have the retanning function.
In the prior art, the oiliness composition of lubricating retanning agent derives from expensive long key Fatty Alcohol(C12-C14 and C12-C18), perhaps only derive from the vegetable and animals oils of iodine number 80～120, compared with prior art the oiliness composition of the present invention's employing is that cheap natural animal-plant oil exchanges and esterification reaction by fat simultaneously, synthesized the reactive behavior height, the oiliness performed polymer that molecular weight is moderate makes that polyreaction is easier carries out.
Technical scheme of the present invention compared with prior art, it is simple to have technology, the characteristics that cost is low, finished product is difficult for layering, the grain side of leather of system is flat thin, and is soft.
Below by embodiment, be described in further detail the present invention, the present invention is not limited only to described embodiment.
Embodiment one:
Adopt prior art, get industrial rape oil 2.0Kg,, add maleic anhydride 1.0Kg again, continued esterification 2 hours, obtain terminal double bond containing grease performed polymer with thanomin 0.6Kg transesterification reaction 2 hours under 125 ℃ of temperature; With NaOH solution the pH value of above-mentioned grease performed polymer is transferred to 7.5, left standstill 0.5 hour, heat up, under agitation disposable adding 1% ammonium persulfate solution 1.0Kg dripped 0.7Kg vinylformic acid in 2 hours, wherein 80 ℃ of polyreactions 3 hours, be warming up to 85 ℃ of polyreactions 1 hour, the cooling reaction product obtains the greasing-retanning agnt of leather of solid resultant 30% to room temperature, and the leather that makes is soft and full.
Embodiment two,
Get Viscotrol C 3.0Kg, the method that adopts embodiment one is synthesized terminal double bond containing grease performed polymer through fat exchange and esterification; With NaOH solution the pH value of above-mentioned grease performed polymer is transferred to 7, left standstill 0.5 hour, heat up, under agitation disposable adding 1% ammonium persulphate liquid 1.2Kg dripped the neutralizer (pH value is 6.5) of 0.8Kg vinylformic acid and 0.4Kg methacrylic acid at 1.5 hours, wherein 75 ℃ of reactions 1 hour, be warming up to 80 ℃ of reactions 2 hours, the cooling reaction product obtains the greasing-retanning agnt of leather of solid content 35% to room temperature, it is flat thin, soft to make grain side of leather.
Embodiment three,
Get lard 3.0Kg, the method that adopts embodiment one is synthesized terminal double bond containing grease performed polymer through fat exchange and esterification; Stir the 1% ammonium persulphate liquid 0 of property adding next time, 9Kg, dripped 1.0Kg vinylformic acid neutralizer (pH value is 6.5) and 0.3Kg vinyl cyanide at 1.6 hours, wherein 80 ℃ of reactions 2 hours, be warming up to 85 ℃ of reactions 2 hours, the cooling reaction product is to room temperature, get the greasing-retanning agnt of leather of solid content 25%, the leather that makes is plentiful, moist.
Embodiment four
Adopt prior art, get industrial soya-bean oil 2.0Kg, the method that adopts embodiment one is synthesized terminal double bond containing grease performed polymer through fat exchange and esterification; With NaOH solution the pH value of above-mentioned grease performed polymer is transferred to 7.5, leave standstill about 0.5 hour, heat up, under agitation disposable adding 1% ammonium persulfate solution 1.1Kg dripped the 0.8Kg vinyl cyanide in 2 hours, wherein 78 ℃ of polyreactions 3.2 hours, be warming up to 85 ℃ of polyreactions 1 hour, the cooling reaction product obtains the greasing-retanning agnt of leather of solid resultant 32% to room temperature, and the leather that makes is soft and full.
Embodiment five,
Get lard 3.0Kg, the method that adopts embodiment one is synthesized terminal double bond containing grease performed polymer through fat exchange and esterification; Stir the 1% ammonium persulphate liquid 1.0Kg of property adding next time, dripped 0.6Kg vinylformic acid, 0.3Kg vinyl cyanide and 0.4Kg methacrylic acid at 1.5 hours, wherein 80 ℃ of reactions 2 hours, be warming up to 85 ℃ of reactions 2 hours, the cooling reaction product is to room temperature, get the greasing-retanning agnt of leather of solid content 25%, the leather that makes is plentiful, moist.
Claims (4)
1, the preparation method of greasing-retanning agnt of leather, be to be basic material with natural animal-plant oil, exchange by fat, esterification, synthetic end contains the grease performed polymer of activated double bonds, it is characterized in that with the persulphate being initiator, carry out grafting, copolymerization and modification, make greasing-retanning agnt of leather by vinylformic acid and derivative thereof and above-mentioned performed polymer;
Above-mentioned natural animal-plant oil is 1: 0.3～0.5 with the weight ratio of vinylformic acid and derivative thereof, and modification by copolymerization is reflected in the aqueous solution carries out, PH=6～8, and temperature of reaction is 70～90 ℃, 3～6 hours time.
2, the preparation method of greasing-retanning agnt of leather according to claim 1 is characterized in that described crude vegetal refers to siccative oil, semi-drying oil, nondrying oil, rape oil, Semen Lini oil, Chinese catalpa oil, soya-bean oil, Viscotrol C, lard.
3, the preparation method of greasing-retanning agnt of leather according to claim 1 is characterized in that described vinylformic acid and derivative thereof are one or more in vinylformic acid, methacrylic acid, the vinyl cyanide.
4, the preparation method of greasing-retanning agnt of leather according to claim 1, the add-on that it is characterized in that described initiator is 0.8%～1.5% of a reaction-ure mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01108632 CN1397650A (en) | 2001-07-16 | 2001-07-16 | Process for preparing greasing-retanning agnt of leather |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01108632 CN1397650A (en) | 2001-07-16 | 2001-07-16 | Process for preparing greasing-retanning agnt of leather |
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| CN1397650A true CN1397650A (en) | 2003-02-19 |
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| CN 01108632 Pending CN1397650A (en) | 2001-07-16 | 2001-07-16 | Process for preparing greasing-retanning agnt of leather |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101457262B (en) * | 2008-12-19 | 2012-06-13 | 温州大学 | Method for preparing leather retanning fat-liquoring agent |
| CN103255243A (en) * | 2013-04-16 | 2013-08-21 | 四川德赛尔化工实业有限公司 | Preparation method of soft acrylic resin leather retanning agent |
| CN104032049A (en) * | 2014-06-19 | 2014-09-10 | 梁晓 | Multifunctional leather fatliquoring agent |
-
2001
- 2001-07-16 CN CN 01108632 patent/CN1397650A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101457262B (en) * | 2008-12-19 | 2012-06-13 | 温州大学 | Method for preparing leather retanning fat-liquoring agent |
| CN103255243A (en) * | 2013-04-16 | 2013-08-21 | 四川德赛尔化工实业有限公司 | Preparation method of soft acrylic resin leather retanning agent |
| CN103255243B (en) * | 2013-04-16 | 2015-01-21 | 四川德赛尔化工实业有限公司 | Preparation method of soft acrylic resin leather retanning agent |
| CN104032049A (en) * | 2014-06-19 | 2014-09-10 | 梁晓 | Multifunctional leather fatliquoring agent |
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| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
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