CN1151275C - Leather retanning agent preparation method - Google Patents
Leather retanning agent preparation methodInfo
- Publication number
- CN1151275C CN1151275C CNB001131583A CN00113158A CN1151275C CN 1151275 C CN1151275 C CN 1151275C CN B001131583 A CNB001131583 A CN B001131583A CN 00113158 A CN00113158 A CN 00113158A CN 1151275 C CN1151275 C CN 1151275C
- Authority
- CN
- China
- Prior art keywords
- leather
- monomer
- tanning agent
- composite tanning
- leather composite
- 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.)
- Expired - Fee Related
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- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The present invention provides a method for preparing a leather auxiliary agent, which comprises the steps that monomers are prepared from 30 to 80 wt% of acrylic acid or methacrylic acid, 0 to 30 wt% of methyl acrylate or acrylonitrile, 10 to 50 wt% of unsaturated aldehyde and water which is 1 to 2 times of the weight of the monomers and prepared into a leather retanning agent by aqueous solution polymerization technology. The retanning agent can enhance the softness, the plumpy hand feeling and the fine granule stripes of leather, and meanwhile, the retanning agent has good filling performance, can enhance the performance of alkali resistance, sweat resistance and washing resistance of the leather, and can be used for the retanning processing of the leather of sofas, the leather of clothes, the leather of shoe uppers, etc.
Description
Technical field
The present invention relates to the preparation method of leather agent, particularly relate to the preparation method of leather composite tanning agent.
Background technology
Leather composite tanning agent is the fine chemistry industry material that is used for the chrome tanned leather retanning in the leather production process, occupies critical role in the tanning chemistry product.Existing leather composite tanning agent is divided into acrylic resin retanning agent and contains aldehyde retanning agent two big classes.Wherein acrylic resin retanning agent is based on acrylic or methacrylic acid, or homopolymerization, oligomerisation or with copolymerization such as ethyl propenoate, vinyl cyanide and make, though they have good filling property and select fillibility, can increase the thickness and the fullness of leather, but because the second-order transition temperature of its polymkeric substance is higher, when tanning, exist the leather body hard inevitably, the coarse shortcoming of grain.And contain the aldehyde retanning agent is low-molecular weight compound based on glutaraldehyde, though the effect that they have is soft, graining is fine and smooth, the flat defective thin, that put easy yellowing for a long time of expensive price, tanning has limited their widespread use.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of leather composite tanning agent, the leather composite tanning agent that obtains can be given leather softness, plentiful feel, fine and smooth graining.Possess simultaneously good filling property again and select fillibility, and can improve alkali resistant, sweat proof, the washing resistance performance of leather, and with low cost, production technique is simple.
Of the present invention day be achieved by the following technical solution:
By (1) acrylic or methacrylic acid, (2) methyl acrylate or vinyl cyanide, (3) unsaturated aldehyde compositing monomer, get leather composite tanning agent by aqueous solution polymerization technology, wherein, acrylic or methacrylic acid account for monomer heavy 30～80%, methyl acrylate or vinyl cyanide account for monomer heavy 0～30%, unsaturated aldehyde account for monomer heavy 10～50%, water is heavy 1～2 times of monomer.
In the such scheme, unsaturated aldehyde is propenal or crotonaldehyde.
Aqueous solution polymerization technology in the such scheme is common process, or selects following technology: earlier will (1) acrylic or methacrylic acid 30～50 ℃ down with 10～30% alkali lye neutralization, to the pH value be 5～7; Add (2) methyl acrylate or vinyl cyanide, (3) unsaturated aldehyde again, and add monomer and weigh 0～0.2% sodium lauryl sulphate, mixed 10～30 minutes down at 30～50 ℃; Add monomer again and weigh 0.2～2% water soluble starter, monomer weighs 0.01～0.2% chain-transfer agent, reacts 3～9 hours down at 40～80 ℃.
In the above-mentioned polymerization technique, alkali lye is the aqueous solution of sodium hydroxide or potassium hydroxide; Water soluble starter is an ammonium persulphate; Chain-transfer agent is a mercaprol.
Embodiment
The prepared retanning agent of the present invention contains carboxyl and aldehyde radical simultaneously owing in the component, thereby can give leather softness, plentiful feel, fine and smooth graining, possesses good filling simultaneously again and selects filling properties, and can improve alkali resistant, the sweat proof of leather.Washing resistance performance, can avoid that pure acrylic resin retanning agent tanning feel plate is hard, graining is sent out thick and tradition contains the tanning of aldehyde retanning agent flat thin, easily yellowing and expensive shortcoming, be the retanning material of a kind of over-all properties and ratio of performance to price excellence, can be owing to the retanning processing of sofa artificial leather, clothing leather, upper leather etc.This retanning agent also can reduce the possibility that chromic salts is washed out in retanning and the later operation in addition, and good environmental protection effect is arranged.
Table one to table four is respectively that the prepared leather composite tanning agent of the present invention is used for thickening effect, soft effect, grain effect and anti-yellowing effect after the tanning.Wherein, according to the feel of doing the soft leather of ura-rate soft effect is divided into 1～5 grade, according to the graining sophistication behind the revolutionary cadre of retanning the grain effect is divided into 1～5 grade, situation according to the leather surface yellowing after illumination of the leather after the retanning also is divided into 1～5 grade with anti-yellowing effect, corresponding respectively very poor, poor, general, good, fine five class.
Table one thickens effect
| The leather composite tanning agent title | Consumption (%) | Pigskin garment leather thickens rate (%) | The buffalo sofa artificial leather thickens rate (%) | ||
| The back | The limit belly | The back | The limit belly | ||
| Leather composite tanning agent of the present invention | 5 | 17.8 | 23.5 | 21.3 | 24.9 |
| The pure acrylic resin retanning agent | 5 | 18.1 | 23.2 | 20.8 | 24.8 |
| Modified glutaraldehyde | 5 | 10.4 | 11.5 | 11.7 | 13.8 |
Table two soft effect
| The leather composite tanning agent title | Not stuffing | Stuffing |
| Leather composite tanning agent of the present invention | 4 | 5 |
| The pure acrylic resin retanning agent | 1 | 3 |
| Modified glutaraldehyde | 4 | 5 |
Table three grain effect
| The leather composite tanning agent title | The grain effect |
| Leather composite tanning agent of the present invention | 4 |
| The pure acrylic resin retanning agent | 3 |
| Modified glutaraldehyde | 5 |
The anti-yellowing effect of table four
| The leather composite tanning agent title | Anti-yellowing effect |
| Leather composite tanning agent of the present invention | 5 |
| The pure acrylic resin retanning agent | 5 |
| Modified glutaraldehyde | 1 |
Be embodiments of the invention below.
Embodiment one
In the 250ml four-necked bottle of band stirring, condenser, add the vinylformic acid of 20.0g and the distilled water of 20.0g, after stirring mixes evenly, slowly dropping sodium solution (4.0g sodium hydroxide+16.0g distilled water is made into) neutralizes, logical water coolant, keep the interior temperature of bottle to be no more than 35 ℃, the pH value for the treatment of mixed liquid becomes at 5.0～7.0 o'clock, stops the hydro-oxidation sodium solution.With the 12.0g crotonaldehyde, 8.0g vinyl cyanide, the distilled water of 0.05g sodium lauryl sulphate and 10.0g add in the four-necked bottle then, and logical nitrogen stirred 30 minutes in 35 ℃.
The mercaprol of 0.4g ammonium persulphate and 0.02g is dissolved in respectively in the 5.0g distilled water, places the material pipe standby more respectively.Be warming up to 75 ℃, treat that temperature steadily dripped ammonium persulphate and mercaprol the back in 1.5 hours.75 ℃ are incubated 2 hours, the 0.4g ammonium persulphate are dissolved in the 5.0g distilled water again, splash into four-necked bottle 1f1 in 15 minutes, are incubated logical water coolant after 1 hour, are cooled to 30 ℃ of dischargings.Promptly making solid content is 38%～42%, viscosity be 500～10000CP (35 ℃) contain aldehyde macromolecule resin retanning agent.
Embodiment two
In the 230ml four-necked bottle of band stirring, condenser, add the methacrylic acid of 24.0g and the distilled water of 20.0g, after stirring mixes evenly, slowly dropping sodium solution (5.0g sodium hydroxide+36.0g distilled water is made into) neutralizes, logical water coolant, keep the interior temperature of bottle to be no more than 40 ℃, the pH value for the treatment of mixed liquid becomes at 5.0～7.0 o'clock, stops the hydro-oxidation sodium solution.With the 4.0g crotonaldehyde, 12.0g methyl acrylate, the distilled water of 0.08g sodium lauryl sulphate and 10.0g add in the four-necked bottle then, and logical nitrogen stirred 30 minutes in 40 ℃.
The mercaprol of 0.4g ammonium persulphate and 0.01g is dissolved in respectively in the 5.0g distilled water, places filling tube standby more respectively.Be warming up to 70 ℃, treat that temperature steadily dripped ammonium persulphate and mercaprol the back in 1.5 hours.70 ℃ are incubated 2 hours, the 0.4g ammonium persulphate are dissolved in the 5.0g distilled water again, splash in the four-necked bottle in 15 minutes, are incubated logical water coolant after 1 hour, are cooled to 30 ℃ of dischargings.
Embodiment three
In the 250ml four-necked bottle of band stirring, condenser, add the vinylformic acid of 12g and the distilled water of 20.0g, after stirring mixes evenly, slowly dropping sodium solution (5.0g sodium hydroxide+16.0g distilled water is made into) neutralizes, logical water coolant, keep the interior temperature of bottle to be no more than 30 ℃, the pH value for the treatment of mixed liquid becomes at 5.0～7.0 o'clock, stops the hydro-oxidation sodium solution.With the 20.0g crotonaldehyde, 8.0g methyl acrylate, the distilled water of 0.04g sodium lauryl sulphate and 10.0g add in the four-necked bottle then, and logical nitrogen stirred 30 minutes in 30 ℃.
The mercaprol of 0.3g ammonium persulphate and 0.08g is dissolved in respectively in the 5.0g distilled water, places filling tube standby more respectively.Be warming up to 40 ℃, treat that temperature steadily dripped ammonium persulphate and mercaprol the back in 2 hours.40 ℃ are incubated 4 hours, the 0.4g ammonium persulphate are dissolved in the 5.0g distilled water again, splash in the four-necked bottle in 1 hour, are incubated logical water coolant after 2 hours, are cooled to 30 ℃ of dischargings.
Embodiment four
In the 250ml four-necked bottle of band stirring, condenser, add the methacrylic acid of 32.0g and the distilled water of 14.0g, after stirring mixes evenly, slowly dripping potassium hydroxide solution (5.0g potassium hydroxide+12.0g distilled water is made into) neutralizes, logical water coolant, keep the interior temperature of bottle to be no more than 50 ℃ of pH values for the treatment of mixed liquid and become at 5.0～7.0 o'clock, stop the hydro-oxidation potassium solution.Then the 8.0g propenal is added in the four-necked bottle, logical nitrogen stirred 10 minutes in 50 ℃.
The mercaprol of 0.06g ammonium persulphate and 0.03g is dissolved in respectively in the 5.0g distilled water, places filling tube standby more respectively.Be warming up to 80 ℃, treat that temperature steadily dripped ammonium persulphate and mercaprol the back in 1 hour.80 ℃ are incubated 1 hour, the 0.02g ammonium persulphate are dissolved in the 5.0g distilled water again, splash in the four-necked bottle in 15 minutes, are incubated logical water coolant after 1 hour, are cooled to 30 ℃ of dischargings.
Claims (4)
1. the preparation method of a leather composite tanning agent, it is characterized in that: by (1) acrylic or methacrylic acid, (2) methyl acrylate or vinyl cyanide, (3) unsaturated aldehyde compositing monomer, get leather composite tanning agent by aqueous solution polymerization technology, wherein, acrylic or methacrylic acid account for monomer heavy 30～80%, methyl acrylate or vinyl cyanide account for monomer heavy 0～30%, unsaturated aldehyde account for monomer heavy 10～50%, water is heavy 1～2 times of monomer.
2. the preparation method of leather composite tanning agent according to claim 1, it is characterized in that: unsaturated aldehyde is propenal or crotonaldehyde.
3. the preparation method of leather composite tanning agent according to claim 1 and 2, it is characterized in that: aqueous solution polymerization technology is common process, or select following technology: earlier will (1) acrylic or methacrylic acid 30～50 ℃ down with 10～30% alkali lye neutralization, to the pH value be 5～7; Add (2) methyl acrylate or vinyl cyanide, (3) unsaturated aldehyde again, and add monomer and weigh 0～0.2% sodium lauryl sulphate, mixed 10～30 minutes down at 30～50 ℃; Add monomer again and weigh 0.2～2% water soluble starter, monomer weighs 0.01～0.2% chain-transfer agent, reacts 3～9 hours down at 40～80 ℃.
4. the preparation method of leather composite tanning agent according to claim 3, it is characterized in that: alkali lye is the aqueous solution of sodium hydroxide or potassium hydroxide; Water soluble starter is an ammonium persulphate: chain-transfer agent is a mercaprol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001131583A CN1151275C (en) | 2000-09-04 | 2000-09-04 | Leather retanning agent preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001131583A CN1151275C (en) | 2000-09-04 | 2000-09-04 | Leather retanning agent preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1341754A CN1341754A (en) | 2002-03-27 |
| CN1151275C true CN1151275C (en) | 2004-05-26 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001131583A Expired - Fee Related CN1151275C (en) | 2000-09-04 | 2000-09-04 | Leather retanning agent preparation method |
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| Country | Link |
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| CN (1) | CN1151275C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101643798B (en) * | 2009-03-03 | 2012-12-19 | 齐河力厚化工有限公司 | Novel auxiliary agent for leather pickling procedure |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100369947C (en) * | 2006-04-20 | 2008-02-20 | 陕西科技大学 | Emulsion grafting copolymerization process of preparing retanning and fat liquoring agent for leather |
| CN101514376B (en) * | 2008-02-22 | 2012-06-06 | 信保贸易实业股份有限公司 | Leather retanning filling agent, method for manufacturing same, method for leather retanning filling |
| CN101787401B (en) * | 2009-01-22 | 2013-08-07 | 中国科学院成都有机化学有限公司 | Preparation method of half aldehyde type high molecular leather retanning agent |
| CN101871024B (en) * | 2009-04-23 | 2013-03-13 | 中国科学院成都有机化学有限公司 | Method for preparing aldehyde-containing polyurethane-acrylate resin tanning agent |
| CN102534060B (en) * | 2011-12-21 | 2014-03-26 | 四川亭江新材料股份有限公司 | Method for preparing re-tanning and fatliquoring agent |
| CN102516444B (en) * | 2011-12-31 | 2013-09-25 | 四川达威科技股份有限公司 | Acrylic resin retanning agent and preparation method thereof |
| CN102586507A (en) * | 2012-03-21 | 2012-07-18 | 陕西科技大学 | Method for preparing acrylic resin modified graphene oxide leather tanning agent |
| CN102628089B (en) * | 2012-03-31 | 2013-08-07 | 陕西科技大学 | Preparation method for graphene oxide-modified sulfited fatliquor |
| CN107151279B (en) * | 2017-06-22 | 2019-03-08 | 陕西科技大学 | Leather retanning agent n-hydroxysuccinimide-polyacrylate and preparation method thereof |
| CN108330227B (en) * | 2018-02-07 | 2020-07-21 | 陕西科技大学 | Amphoteric polymer chrome-free tanning agent and preparation method thereof |
| CN111961768B (en) * | 2020-07-24 | 2023-07-28 | 汤普勒新材料嘉兴有限公司 | Preparation method of amphoteric polyacrylic acid retanning agent |
-
2000
- 2000-09-04 CN CNB001131583A patent/CN1151275C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101643798B (en) * | 2009-03-03 | 2012-12-19 | 齐河力厚化工有限公司 | Novel auxiliary agent for leather pickling procedure |
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| CN1341754A (en) | 2002-03-27 |
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