CN101871023B - Method for preparing acid-resistance polyurethane-acrylic resin retanning agent - Google Patents
Method for preparing acid-resistance polyurethane-acrylic resin retanning agent Download PDFInfo
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- CN101871023B CN101871023B CN 200910059037 CN200910059037A CN101871023B CN 101871023 B CN101871023 B CN 101871023B CN 200910059037 CN200910059037 CN 200910059037 CN 200910059037 A CN200910059037 A CN 200910059037A CN 101871023 B CN101871023 B CN 101871023B
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Abstract
The invention provides a method for preparing an acid-resistance polyurethane-acrylic resin retanning agent. In the method, acrylic acid or methacrylic acid which accounts for 50 to 80 percent of the total weight of monomers, polymerizable non-ionic polyurethane oligomer which accounts for 15 to 40 percent of the total weight of the monomers and is prepared by a specific method and methyl acrylate or acrylonitrile which accounts for 5 to 30 percent of the total weight of the monomers are dissolved in distilled water in an amount which is 1 to 5 times the total weight of the monomers to form the acid-resistance polyurethane-acrylic resin retanning agent through free radical copolymerization. The retanning agent has high selective fallibility, and offers a soft and full handfeel and fine granular texture to leather. Moreover, the retanning agent can be used in a low pH-value environment in the last stage of chromium tanning or chromium retanning to promote the absorption and fixation of a chromium tanning and obviously reduce the chromium salt content of chromium tanning waste liquid obviously, and thus the pollution caused by the tanning waste liquid to the environment greatly. The acid-resistance polyurethane-acrylic resin retanning agent is a novel multifunctional environmentally-friendly leather retanning material and is suitable to be used for the retanning processing of garment leather, shoe upper leather, sofa leather and the like.
Description
Technical field
The present invention relates to a kind of preparation method of leather chemical industry auxiliary agent, particularly relate to the preparation of acid-resistance polyurethane-acrylic resin retanning 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 an important position in the leather chemical industry auxiliary agent.As an important class leather retanning material, the macromolecule resin retanning agent is large owing to having molecular weight, institute's band effect group is numerous, and the advantages such as the molecular structure height is adjustable, can give the good Selective filling of finished leather and sense of fullness, thereby in all kinds of leather tanning processes, obtain a wide range of applications, and be expected to play a significant role in the process hides pollution of chromium prevents by suitable molecular designing, promote the production process that cleans of tanning industry.
Acrylic resin retanning agent is the macromolecule resin retanning agent that present tanning industry consumption is maximum, purposes is the widest, it is as main body take acrylic or methacrylic acid, by radically homo, each other copolymerization or get with copolymerization such as methyl acrylate, vinyl cyanide, have good Selective filling, can significantly increase thickness and the sense of fullness of leather.Simultaneously on the acrylic resin retanning agent molecular chain with the carboxyl that can be combined with chrome tanning agent, can be effectively fixing chrome tanning agent, avoid chrome tanning agent in retanning and process hides operation subsequently, to be washed out, can play the effect that reduces chromic salts content in the leather-making waste water, have obvious environment protection significance.
Provide because acrylic resin retanning agent water-soluble is the carboxylate radical by anionic property, carboxylate radical will be converted into carboxyl in low pH value (pH≤3.8) environment, make acrylic resin retanning agent lose wetting ability and precipitate.Usually the leather chrome tanning later stage not yet in and the time its collegen filament inside the pH value be 3.8～4.2, as not introducing special hydrophilic radical (such as nonionic and cationic hydrophilic radical), existing anionic property acrylic resin retanning agent can't effectively be penetrated into leather collagen fiber inside, thereby the retanning process after can only being used for neutralizing, can not in chrome tanning or the low ph environment in chromium retanning later stage, use, can't give full play to it to the absorption fixed function of chrome tanning agent excellence in the highest tanning stage of these chromic salts content, realize alleviating to greatest extent the target of pollution of chromium.In addition, the second-order transition temperature of acrylic resin retanning agent is higher, and also unavoidably there are the defectives such as the body bone hardens, grain is coarse in the leather of institute's retanning.
The Polyurethane Retanning agent is the high molecular retanning agent that a class has certain purposes, and it is to get through stepwise polymerization reaction by polyisocyanates and polyol compound.Because molecular structure is similar to the molecular structure of hide collagen, and tool height adjustability, the Polyurethane Retanning agent not only has natural feel, the fine and smooth graining that keeps leather and gives finished leather with outside toughness preferably and the advantage such as flexible, also can make it to have characteristic that acrylic resin retanning agent does not possess by molecular designing, as introduce the polyoxyethylene segment of nonionic, can make the Polyurethane Retanning agent have good acid resistance and help the function of other Retanning Materials, dyestuff, grease uniformly penetrating.Yet the Polyurethane Retanning agent is generally oligopolymer, and molecular weight is not high enough, exists fillibility poor, the flat defective such as thin of finished leather, and expensive, limited being widely used of it.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of new acid-resistance polyurethane-acrylic resin retanning agent, make the leather composite tanning agent that makes that good Selective filling not only be arranged, and can give the graining of the soft and full feel of leather, exquisiteness, and can in chrome tanning and the low ph environment in chromium retanning later stage, use, help the absorption of chrome tanning agent to fix, can obviously reduce chromic salts content in the chroming waste liquor, thereby significantly alleviate the tanning waste liquid to the pollution of environment.
The objective of the invention is to realize by the following technical solutions:
Polymerizable nonionic polyurethane oligomer, (3) methyl acrylate or vinyl cyanide compositing monomer that sour by (1) acrylic or methacrylic, (2) prepare by ad hoc approach, make the multifunction environment-protection type leather composite tanning agent by aqueous solution polymerization, wherein: acrylic or methacrylic acid accounts for 50～80% of monomer weight, polymerizable nonionic polyurethane oligomer by the ad hoc approach preparation accounts for 15～40% of monomer weight, methyl acrylate or vinyl cyanide account for 5～30% of monomer weight, and distilled water is 1～5 times of monomer weight.
In the such scheme, polymerizable nonionic polyurethane oligomer is the polymerizable nonionic polyurethane oligomer by the ad hoc approach preparation, its specific preparation method is: will add with the Soxylat A 25-7 of end-vinyl first, be warmed up to 50～80 ℃, add monomer and weigh 0.01～0.2% oil-soluble catalyst, after mixing 10～30 minutes, add vulcabond, reacted 2～4 hours, then add polyethenoxy ether, continue reaction 3～5 hours, cooling namely gets polymerizable nonionic polyurethane oligomer.Wherein: used oil-soluble catalyst is dibutyl tin laurate in the polymerization technique; Number-average molecular weight with the Soxylat A 25-7 of end-vinyl is 400～2,000; The number-average molecular weight of polyethenoxy ether is 400～2,000; The number-average molecular weight of prepared polymerizable nonionic polyurethane oligomer is 800～5,000.
In the such scheme, described aqueous solution polymerization technique is conventional polymerization technique, perhaps select following technique: first the acid of (1) acrylic or methacrylic being regulated the pH value with 10～30% alkali lye is 3.2～7.0, the temperature of controlling reaction solution therebetween is 30～50 ℃, and then polymerizable nonionic polyurethane oligomer, (3) methyl acrylate or the vinyl cyanide of the preparation of adding (2) ad hoc approach, mix and blend 10～30 minutes, the water soluble starter that adds monomer weight 0.1～5% was 40～90 ℃ of lower reactions 2～8 hours.Wherein: alkali lye is sodium hydroxide or potassium hydroxide aqueous solution; Water soluble starter is Potassium Persulphate or ammonium persulphate.
The present invention participates in free-radical polymerized by specific polymerizable nonionic polyurethane oligomer, the urethane segment of nonionic is introduced acrylic resin, the leather retanning material that makes has the advantage of acrylic resin retanning agent and Polyurethane Retanning agent concurrently, both possessed the good Selective filling of acrylic resin, can give again leather soft and full feel, fine and smooth graining, can effectively avoid pure acrylic resin retanning agent tanning plate hard, grain is coarse and Polyurethane Retanning agent tanning is flat thin, expensive shortcoming, be the leather retanning material of a kind of over-all properties and ratio of performance to price excellence, can be used for the dress leather, upper leather, the retanning processing of sofa artificial leather etc.While is because of the introducing of nonionic segment, strengthened its acidproof and penetrating power, make it and in chrome tanning and the low ph environment in chromium retanning later stage, to use, can give full play on it with the absorption fixed action of carboxyl to chromic salts, help the absorption of chrome tanning agent to fix, can obviously reduce chromic salts content in the chroming waste liquor, significantly alleviate the tanning waste liquid to the pollution of environment, have good environmental protection effect.
Embodiment
Embodiment one
The instruments such as 250ml four-necked bottle, agitator, filling tube in 120 ℃ of dryings 2 hours, are taken out and place moisture eliminator to cool off.To being 1 with the molecular weight that adds 20.0g in the 250ml four-necked bottle of agitator, thermometer, 000 Soxylat A 25-7 with end-vinyl, be heated to 80 ℃ under stirring, the dibutyl tin laurate that adds 0.01g, mix 10 minutes, then drip the toluene two different hydrogen acid ethers (TDI) of 3.48g.Adding the 20.0g molecular weight behind the reaction 2h is 1,000 polyoxy and alkene ether again, continues reaction 2h.Then be cooled to 30 ℃, discharging namely makes polymerizable nonionic polyurethane oligomer.
With stirring, adding 15.0g vinylformic acid and 30.0g distilled water in the 250ml four-necked bottle of condenser, mix, then slowly drip concentration and be 20% sodium hydroxide solution, regulating the pH value is 4.0, the temperature of controlling reaction solution therebetween is 30 ℃.Then add 10g polymerizable nonionic polyurethane oligomer and 5g vinyl cyanide in this reaction solution, logical nitrogen deoxygenation also stirred 20 minutes.Get the 0.12g ammonium persulphate and be dissolved in the 10g distilled water, place filling tube for subsequent use.Reacting liquid temperature is risen to 70 ℃ and drip ammonium persulfate solution, in 1.5 hours, dropwise, again insulation 2 hours under this temperature.Again the 0.12g ammonium persulphate is dissolved in the 10g distilled water, and in 15 minutes, is added drop-wise in the reaction solution, again be incubated 1 hour and can be cooled to 30 ℃ of dischargings.Namely making solid content is 35～40%, and viscosity is the acid-resistance polyurethane-acrylic resin retanning agent of 500～5,000cp (30 ℃).
Embodiment two
The instruments such as 250ml four-necked bottle, agitator, filling tube in 120 ℃ of dryings 2 hours, are taken out and place moisture eliminator to cool off.To being 400 Soxylat A 25-7s with end-vinyl with the molecular weight that adds 8.0g in the 250ml four-necked bottle of agitator, thermometer, be heated to 75 ℃ under stirring, the dibutyl tin laurate that adds 0.02g, mix 10 minutes, then drip the toluene two different hydrogen acid ethers (TDI) of 3.48g.Adding the 8.0g molecular weight behind the reaction 2h is 400 polyethenoxy ethers again, continues reaction 2h.Then be cooled to 30 ℃ of dischargings, namely make polymerizable nonionic polyurethane oligomer.
With stirring, adding 32.0g methacrylic acid and 40.0g distilled water in the 250ml four-necked bottle of condenser, mix, then slowly drip concentration and be 30% sodium hydroxide solution, regulating the pH value is 5.5, the temperature of controlling reaction solution therebetween is 35 ℃.Then add 6g polymerizable nonionic polyurethane oligomer and 2g methyl acrylate in this reaction solution, logical nitrogen deoxygenation also stirred 20 minutes.Get the 0.4g ammonium persulphate and be dissolved in the 10g distilled water, place filling tube for subsequent use.Reacting liquid temperature is risen to 70 ℃ and drip ammonium persulfate solution, in 1.5 hours, dropwise, again insulation 2 hours under this temperature.Again the 0.4g ammonium persulphate is dissolved in the 10g distilled water, and in 15 minutes, is added drop-wise in the reaction solution, again be incubated 1 hour and can be cooled to 30 ℃ of dischargings.Namely making solid content is 35～40%, and viscosity is the acid-resistance polyurethane-acrylic resin retanning agent of 500～5,000cp (30 ℃).
Embodiment three
The instruments such as 250ml four-necked bottle, agitator, filling tube in 120 ℃ of dryings 2 hours, are taken out and place moisture eliminator to cool off.To being 1 with the molecular weight that adds 10.0g in the 250ml four-necked bottle of agitator, thermometer, 000 Soxylat A 25-7 with end-vinyl, be heated to 70 ℃ under stirring, the dibutyl tin laurate that adds 0.02g, mix 10 minutes, then drip the toluene two different hydrogen acid ethers (TDI) of 1.74g.Adding the 20.0g molecular weight behind the reaction 2h is 2,000 polyethenoxy ethers again, continues reaction 2h.Then be cooled to 30 ℃ of dischargings, namely make polymerizable nonionic polyurethane oligomer.
In with the 250ml four-necked bottle of stirring, condenser, add 12.0g vinylformic acid, 6.0g methacrylic acid and 30.0g distilled water, mix, then slowly drip concentration and be 20% potassium hydroxide solution, regulating the pH value is 6.0, and the temperature of controlling reaction solution therebetween is 30 ℃.Then add 9g polymerizable nonionic polyurethane oligomer and 3g vinyl cyanide in this reaction solution, logical nitrogen deoxygenation also stirred 20 minutes.Get the 0.15g Potassium Persulphate and be dissolved in the 10g distilled water, place filling tube for subsequent use.Reacting liquid temperature is risen to 80 ℃ and drip potassium persulfate solution, in 1.5 hours, dropwise, again insulation 2 hours under this temperature.Again the 0.15g Potassium Persulphate is dissolved in the 10g distilled water, and in 15 minutes, is added drop-wise in the reaction solution, again be incubated 1 hour and can be cooled to 30 ℃ of dischargings.Namely making solid content is 35～40%, and viscosity is the acid-resistance polyurethane-acrylic resin retanning agent of 500～5,000cp (30 ℃).
Embodiment four
The instruments such as 250ml four-necked bottle, agitator, filling tube in 120 ℃ of dryings 2 hours, are taken out and place moisture eliminator to cool off.To being 1 with the molecular weight that adds 20.0g in the 250ml four-necked bottle of agitator, thermometer, 000 Soxylat A 25-7 with end-vinyl, be heated to 70 ℃ under stirring, the dibutyl tin laurate that adds 0.02g, mix 10 minutes, then drip the toluene two different hydrogen acid ethers (TDI) of 1.74g.Adding the 4.0g molecular weight behind the reaction 2h is 400 polyethenoxy ethers again, continues reaction 2h.Then be cooled to 30 ℃ of dischargings, namely make polymerizable nonionic polyurethane oligomer.
In with the 250ml four-necked bottle of stirring, condenser, add 4.0g vinylformic acid, 11.0g methacrylic acid and 30.0g distilled water, mix, then slowly drip concentration and be 20% sodium hydroxide solution, regulating the pH value is 5.5, and the temperature of controlling reaction solution therebetween is 30 ℃.Then add 12g polymerizable nonionic polyurethane oligomer and 3g methyl acrylate in this reaction solution, logical nitrogen deoxygenation also stirred 20 minutes.Get the 0.2g ammonium persulphate and be dissolved in the 10g distilled water, place filling tube for subsequent use.Reacting liquid temperature is risen to 75 ℃ and drip ammonium persulfate solution, in 1.5 hours, dropwise, again insulation 2 hours under this temperature.Again the 0.2g ammonium persulphate is dissolved in the 10g distilled water, and in 15 minutes, is added drop-wise in the reaction solution, again be incubated 1 hour and can be cooled to 30 ℃ of dischargings.Namely making solid content is 35～40%, and viscosity is the acid-resistance polyurethane-acrylic resin retanning agent of 500～5,000cp (30 ℃).
Claims (8)
1. the preparation method of an acid-resistance polyurethane-acrylic resin retanning agent is characterized in that: make multifunction environment-protection type leather composite tanning agent by polymerizable nonionic polyurethane oligomer, (3) methyl acrylate or the vinyl cyanide of ad hoc approach preparation by aqueous solution polymerization by the acid of (1) acrylic or methacrylic, (2); Wherein, acrylic or methacrylic acid accounts for 50～80% of monomer weight, polymerizable nonionic polyurethane oligomer by the ad hoc approach preparation accounts for 15～40% of monomer weight, and methyl acrylate or vinyl cyanide account for 5～30% of monomer weight, and distilled water is 1～5 times of monomer weight; Polymerizable nonionic polyurethane oligomer, (3) methyl acrylate or vinyl cyanide compositing monomer that described monomer is prepared by ad hoc approach by the acid of (1) acrylic or methacrylic, (2); The ad hoc approach of described polymerizable nonionic polyurethane oligomer is prepared as first and will adds with the Soxylat A 25-7 of end-vinyl, be warmed up to 50～80 ℃, add monomer and weigh 0.01～0.2% oil-soluble catalyst, after mixing 10～30 minutes, add vulcabond, reacted 2～4 hours, then add polyethenoxy ether, continue reaction 3～5 hours, cooling namely gets polymerizable nonionic polyurethane oligomer.
2. the preparation method of a kind of acid-resistance polyurethane-acrylic resin retanning agent according to claim 1 is characterized in that: the number-average molecular weight with the Soxylat A 25-7 of end-vinyl is 400～2,000.
3. the preparation method of a kind of acid-resistance polyurethane-acrylic resin retanning agent according to claim 1, it is characterized in that: the number-average molecular weight of polyethenoxy ether is 400～2,000.
4. the preparation method of a kind of acid-resistance polyurethane-acrylic resin retanning agent according to claim 1, it is characterized in that: the number-average molecular weight of prepared polymerizable nonionic polyurethane oligomer is 800～5,000.
5. the preparation method of a kind of acid-resistance polyurethane-acrylic resin retanning agent according to claim 1, it is characterized in that: used oil-soluble catalyst is dibutyl tin laurate in the polymerization technique.
6. the preparation method of a kind of acid-resistance polyurethane-acrylic resin retanning agent according to claim 1, it is characterized in that: described aqueous solution polymerization technique is conventional polymerization technique, perhaps select following technique: first the acid of (1) acrylic or methacrylic being regulated the pH value with 10～30% alkali lye is 3.2～7.0, the temperature of controlling reaction solution therebetween is 30～50 ℃, and then the polymerizable nonionic polyurethane oligomer of adding (2) ad hoc approach preparation, (3) methyl acrylate or vinyl cyanide, mix and blend 10～30 minutes, the water soluble starter that adds monomer weight 0.1～5% was 40～90 ℃ of lower reactions 2～8 hours.
7. the preparation method of a kind of acid-resistance polyurethane-acrylic resin retanning agent according to claim 6, it is characterized in that: the alkali lye in the described polymerization technique is sodium hydroxide or potassium hydroxide aqueous solution.
8. the preparation method of a kind of acid-resistance polyurethane-acrylic resin retanning agent according to claim 6, it is characterized in that: the water soluble starter in the described polymerization technique is Potassium Persulphate or ammonium persulphate.
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| CN 200910059037 CN101871023B (en) | 2009-04-23 | 2009-04-23 | Method for preparing acid-resistance polyurethane-acrylic resin retanning agent |
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| CN 200910059037 CN101871023B (en) | 2009-04-23 | 2009-04-23 | Method for preparing acid-resistance polyurethane-acrylic resin retanning agent |
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| CN101871023B true CN101871023B (en) | 2013-01-02 |
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| CN102212625B (en) * | 2011-04-19 | 2013-07-10 | 陕西科技大学 | Amphoteric vinyl copolymer retanning agent and preparation method thereof |
| CN104073575B (en) * | 2014-07-16 | 2016-07-06 | 四川大学 | Fur tanning agent based on isocyanates and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1307139A (en) * | 2000-01-27 | 2001-08-08 | 安徽大学 | High molecular metal complex leather tanning agent and preparing method thereof |
| CN1492057A (en) * | 2003-09-23 | 2004-04-28 | 杭州水乡渔业有限公司 | Tanning method for fish skin and after finishing method for fish skin leather |
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| US20050123781A1 (en) * | 2003-12-04 | 2005-06-09 | Drescher James C. | One-component flexible etch resistant clearcoat |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1307139A (en) * | 2000-01-27 | 2001-08-08 | 安徽大学 | High molecular metal complex leather tanning agent and preparing method thereof |
| CN1492057A (en) * | 2003-09-23 | 2004-04-28 | 杭州水乡渔业有限公司 | Tanning method for fish skin and after finishing method for fish skin leather |
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