CN101871024B - Method for preparing aldehyde-containing polyurethane-acrylate resin tanning agent - Google Patents
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Abstract
The invention relates to a method for preparing an aldehyde-containing polyurethane-acrylate resin tanning agent. The aldehyde-containing polyurethane-acrylate resin tanning agent is prepared from a polymerizable nonionic polyurethane oligomer and unsaturated aldehyde by carrying out radical copolymerization in distilled water. The tanning agent contains aldehyde group, can be combined with a covalent bond of hide collagen fibers, has obvious tanning function, can make leather obtain higher hydrothermal stability when reducing the use amount of a chrome tanning agent, has excellent selective filling property, can make the leather have soft and plump hand feeling and exquisite grain, can be assorted with the chrome tanning agent to use in the low pH value environment of chrom tanning and chrome retanning, is favorable to adsorption fixation of the chrome tanning agent, can obviously reduce content of chromium salt in chrom tanning liquid waste so as to greatly reduce pollution of the tanning liquid waste to the environment, is a novel multifunctional environment-friendly leather tanning material and is suitable for tanning processing of sofa leather, instep leather, clothing 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 the polyurethane-acrylate resin tanning agent that contains aldehyde radical.
Technical background
The leather tanning material refer to can with rawhide collegen filament generation strong interaction, thereby improve the stability of materials with hide glue fibril bundle, rawhide is converted into leather, make it to possess the Leather Chemicals of higher hydrothermal stability.The leather tanning material is a class chemical materials of most critical in the tanning industry, and the height of its performance has directly determined the quality of prepared leather.
Leather retanning agent can be divided into inorganic tanning agent and organic tanning agent two large classes according to chemical ingredients.Most importantly alkali formula chromic salt (chrome tanning agent) in the inorganic tanning agent also has the inorganic polyacid salt compounds such as zirconium, aluminium, iron and other metallic compound and silicate, phosphoric acid salt in addition.Organic tanning agent then mainly comprises: vegetable tanning agent, synthetic tanning agent, aldehyde tanning agent, polymer tanning agent etc.What use morely in the tanning industry at present is chromic salts tanning agent, vegetable tanning agent and polymer tanning agent.
Acrylic resin is as main body take acrylic or methacrylic acid, by radically homo, each other copolymerization or the macromolecule resin that gets with other unsaturated monomer copolymerization such as methyl acrylate, vinyl cyanide, it is large to have molecular weight, and institute's band effect group is many, and the advantage such as the molecular structure height is adjustable.There is not chemical bonds between general acrylic resin and materials with hide glue fibril, mainly be to participate in tannery by Physical interaction, raising helps very limited to the materials with hide glue fibril hydrothermal stability, so normally as Retanning Materials, the good Selective filling of finished leather and sense of fullness can be given, the thickness of leather can be significantly increased.Simultaneously on the acrylic resin 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.
In view of the compound that contains aldehyde radical can to produce chemical bond crosslinked with materials with hide glue fibril, have preferably flexibility, so there is at present research that aldehyde radical is introduced acrylic resin, contain the acrylate resin tanning agent of aldehyde radical with preparation, make it to have certain flexibility, can be at the hydrothermal stability that to a certain degree improves leather.Disclose a kind of preparation method of leather composite tanning agent such as Chinese invention patent 003158.3, by the copolymerization of acrylic or methacrylic acid with methyl acrylate, vinyl cyanide and unsaturated aldehyde, obtained to contain the acrylic resin retanning agent of aldehyde radical.This contain aldehyde radical acrylic resin retanning agent can by on the molecular chain the aldehyde radical of being with and materials with hide glue fibril produce covalently cross-linkedly, play the tanning effect.
By the preparation of this patent disclosure technology contain the aldehyde acrylic resin retanning agent water-soluble be that carboxylate radical by anionic property provides, carboxylate radical will be converted into carboxyl in low pH value (pH≤3.8) environment, make it lose wetting ability and precipitate.Usually the leather chrome tanning stage not yet in and the time its collegen filament inside the pH value be 3.0～4.2, as not introducing special hydrophilic radical (such as nonionic and cationic hydrophilic radical), this contains the aldehyde acrylic resin 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 its tanning effect and to the absorption fixed function of chrome tanning agent excellence, realize alleviating to greatest extent the target of pollution of chromium in the highest tanning stage of these chromic salts content.In addition, this second-order transition temperature that contains the aldehyde acrylic resin is higher, and also unavoidably there are the defectives such as the body bone hardens, grain is coarse in the leather of institute's tanning.
Urethane resin is to get through stepwise polymerization reaction by polyisocyanates and polyol compound, uses mainly as retanning agent in the leather tanning process, and molecular weight is generally not high.Because the molecular structure of urethane resin is similar to the molecular structure of collagen, and tool height adjustability, make it not only to have natural feel, the fine and smooth graining that keeps leather and give finished leather with outside toughness preferably and the advantage such as flexible, also can have characteristic that acrylic resin does not possess by molecular designing, as introduce the polyoxyethylene segment of nonionic, can make urethane resin have good acid resistance and help the function of other material uniformly penetrating.Yet as previously mentioned, the urethane resin 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 the polyurethane-acrylate resin tanning agent that contains aldehyde radical newly, make the leather retanning agent that makes to occur covalently cross-linked with materials with hide glue fibril, has certain tanning effect, can when reducing the chrome tanning agent consumption, make leather obtain higher hydrothermal stability.In addition, this polyurethane-acrylate resin tanning agent that contains aldehyde radical has good Selective filling, and can give the graining of the soft and full feel of leather, exquisiteness, and can in the low ph environment of chrome tanning and chromium retanning, be used with chrome tanning agent, can reduce the consumption of chrome tanning agent, help the absorption of chrome tanning agent to fix, can obviously reduce chromic salts content in the chroming waste liquor, thereby significantly alleviate tannery to the pollution of environment.
The objective of the invention is to realize by the following technical solutions:
Polymerizable nonionic polyurethane oligomer, (3) unsaturated aldehyde 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 50～75% of monomer weight, polymerizable nonionic polyurethane oligomer by the ad hoc approach preparation accounts for 15～40% of monomer weight, unsaturated aldehyde accounts for 10～30% 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: be that 10～30% alkali lye adjusting pH value is 3.2～7.0 with (1) acrylic or methacrylic acid with concentration first, the temperature of controlling reaction solution therebetween is 30～50 ℃, and then polymerizable nonionic polyurethane oligomer, (3) unsaturated aldehyde 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 passes through unsaturated aldehyde, specific polymerizable nonionic polyurethane oligomer participates in free-radical polymerized, with aldehyde radical, the urethane segment of nonionic is introduced acrylic resin, the polymer copolymerization resin that makes contains aldehyde radical, can produce covalently cross-linked with materials with hide glue fibril, has the tanning effect, and have simultaneously the advantage of acrylic resin and urethane resin concurrently, namely 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 tanning plate hard, grain is coarse and the urethane tanning is flat thin, expensive shortcoming, can use separately or be used with chrome tanning agent, can reduce the consumption of chrome tanning agent, be the leather tanning 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 the low ph environment of chrome tanning and chromium retanning, to be used with chrome tanning agent, give full play on it with the absorption fixed action of carboxyl to chromic salts, can reduce the consumption of chrome tanning agent, 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 3h is 1,000 polyethenoxy ether again, continues reaction 4h.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 crotonaldehyde in this reaction solution, logical nitrogen deoxygenation also stirred 15 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 2.0 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 polyurethane-acrylate resin tanning agent that contains aldehyde radical of 200～3,000cp (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 5h.Then be cooled to 30 ℃ of dischargings, namely make polymerizable nonionic polyurethane oligomer.
With stirring, adding 30.0g 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 4g propenal 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 2.0 hours, dropwise, again insulation 2 hours under this temperature.Again the 0.4g ammonium persulphate is dissolved in the 10g distilled water, and in 30 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 polyurethane-acrylate resin tanning agent that contains aldehyde radical of 200～3,000cp (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 3h is 2,000 polyethenoxy ethers again, continues reaction 3h.Then be cooled to 30 ℃ of dischargings, namely make polymerizable nonionic polyurethane oligomer.
In with the 250ml four-necked bottle of stirring, condenser, add 10.0g 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 5g crotonaldehyde 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 2.0 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 polyurethane-acrylate resin tanning agent that contains aldehyde radical of 200～3,000cp (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 5h.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 10g polymerizable nonionic polyurethane oligomer and 5g crotonaldehyde 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 2.0 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 polyurethane-acrylate resin tanning agent that contains aldehyde radical of 200～3,000cp (30 ℃).
Claims (9)
1. preparation method who contains the polyurethane-acrylate resin tanning agent of aldehyde radical, it is characterized in that: by the acid of (1) acrylic or methacrylic, (2) the polymerizable nonionic polyurethane oligomer for preparing by ad hoc approach, (3) unsaturated aldehyde makes the multifunction environment-protection type leather retanning agent by aqueous solution polymerization technique, wherein: acrylic or methacrylic acid accounts for 50～75% of monomer weight, polymerizable nonionic polyurethane oligomer by the ad hoc approach preparation accounts for 15～40% of monomer weight, unsaturated aldehyde accounts for 10～30% of monomer weight, and distilled water is 1～5 times of monomer weight; The ad hoc approach of above-mentioned preparation polymerizable nonionic polyurethane oligomer 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.
2. a kind of preparation method who contains the polyurethane-acrylate resin tanning agent of aldehyde radical according to claim 1, it is characterized in that: unsaturated aldehyde is propenal or crotonaldehyde.
3. a kind of preparation method who contains the polyurethane-acrylate resin tanning agent of aldehyde radical 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.
4. a kind of preparation method who contains the polyurethane-acrylate resin tanning agent of aldehyde radical according to claim 1, it is characterized in that: the number-average molecular weight of polyethenoxy ether is 400～2,000.
5. a kind of preparation method who contains the polyurethane-acrylate resin tanning agent of aldehyde radical according to claim 1, it is characterized in that: the number-average molecular weight of prepared polymerizable nonionic polyurethane oligomer is 800～5,000.
6. a kind of preparation method who contains the polyurethane-acrylate resin tanning agent of aldehyde radical according to claim 1, it is characterized in that: used oil-soluble catalyst is dibutyl tin laurate in the polymerization technique.
7. a kind of preparation method who contains the polyurethane-acrylate resin tanning agent of aldehyde radical according to claim 1, it is characterized in that: described aqueous solution polymerization technique is conventional polymerization technique, perhaps select following technique: be that 10～30% alkali lye adjusting pH value is 3.2～7.0 with (1) acrylic or methacrylic acid with concentration first, 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) unsaturated aldehyde, 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.
8. a kind of preparation method who contains the polyurethane-acrylate resin tanning agent of aldehyde radical according to claim 7, it is characterized in that: the alkali lye in the described polymerization technique is sodium hydroxide or potassium hydroxide aqueous solution.
9. a kind of preparation method who contains the polyurethane-acrylate resin tanning agent of aldehyde radical according to claim 7, it is characterized in that: the water soluble starter in the described polymerization technique is Potassium Persulphate or ammonium persulphate.
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| CN102168153B (en) * | 2011-03-28 | 2013-06-19 | 杭州奇达皮革有限公司 | Processing method of seawater-proof vamp leather |
| CN102212625B (en) * | 2011-04-19 | 2013-07-10 | 陕西科技大学 | Amphoteric vinyl copolymer retanning agent and preparation method thereof |
| CN102628089B (en) * | 2012-03-31 | 2013-08-07 | 陕西科技大学 | Preparation method for graphene oxide-modified sulfited fatliquor |
| CN107674193B (en) * | 2017-09-30 | 2019-12-20 | 中国科学院福建物质结构研究所 | Aldehyde functional polyether polyol and preparation method and application thereof |
| CN110204679B (en) * | 2019-05-20 | 2021-08-31 | 齐鲁工业大学 | Preparation method of modified environment-friendly waterborne polyurethane and polyurethane prepared by same |
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| CN1341754A (en) * | 2000-09-04 | 2002-03-27 | 中国科学院成都有机化学研究所 | Leather retanning agent preparation method |
| CN101225451A (en) * | 2008-01-21 | 2008-07-23 | 陕西科技大学 | Terminal aldehyde hyper branched polymer leather retanning agent and preparation method thereof |
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