CN1317396C - Leather tanning agent of modified aminoresin and preparation method thereof - Google Patents
Leather tanning agent of modified aminoresin and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a modified amine resin leather tanning agent which is prepared by a condensation reaction of sulfonated amine resin and protein degradation products in a liquid state or in a powder state. The tanning agent is prepared from 100 parts by weight of formaldehyde, 50 to 100 parts by weight of amido monomer, 50 to 200 parts by weight of sulfonating agent, 25 to 200 parts by weight of protein degradation product solution and 50 to 200 parts by weight of deionized water. The technological steps comprise the preparation of sulfonated amine resin and the condensation reaction of the sulfonated amine resin and the protein degradation products. The content of free formaldehyde in the modified amine resin leather tanning agent is less than 0.3%, and the minimum content can reach 0.03%. The modified amine resin leather tanning agent is applied to leather manufacture, and the content of formaldehyde in the manufactured finished leather is less than 10 mg/kg. Compared with the conventional amine resin leather tanning agent, the performance indexes of the filling property, the plumpy elasticity, the flexibility, the grain surface compactability, etc. of the leather are obviously enhanced, and the water absorption of the leather is obviously reduced.
Description
Technical field
The invention belongs to leather chemical industry material technology field, particularly a kind of leather tanning agent of modified aminoresin and preparation method thereof.
Background technology
Aminoresin is that to contain amino monomer with trimeric cyanamide, Dyhard RU 100, urea etc. be main raw material, the high polymer that forms with the formaldehyde reaction polycondensation.Aminoresin has promptly generally been adopted by tannery all over the world since nineteen thirty generation as leather retanning agent.With full, the smooth consolidation of finished leather after the aminoresin retanning, demonstrate good selection filling properties; But leather softness is not good enough, and suction is fast, water regain is big.Aminoresin combine with collegen filament also can form gradually fine and close crosslinked make the finished leather rerum natura degenerate (Dan Zhihua compiles, the tanning technology volume two, Science Press, 1999:17).
Except that the problems referred to above, free formaldehyde content height can discharge formaldehyde gas deleterious, strong and stimulating in the conventional BMU during use, and the serious harm operator's is healthy, and brings pollution to environment.The leather that utilizes the high leather chemical industry material of these formaldehyde content to make, its formaldehyde content also is in higher level.Because formaldehyde is to the serious harm of human body, formaldehyde content problem in the leather causes the attention of more and more national, many countries have formulated limitation standard to the formaldehyde content in the leather, stipulate as Germany: the shoemaking industry formaldehyde content＜150mg/kg of leather, upholstery leather＜150mg/kg (Liu Xiankui etc., formaldehyde content is measured Review of Problems, Chinese leather in the leather, 2004,33 (1): 39-41).
In order to improve the performance of BMU, people constantly inquire into the modification of BMU, but the leather tanning agent of modified aminoresin that existing method of modifying is obtained generally is in a certain respect a performance to be improved, for example, carry out etherificate with polyphenol, hydroxycarboxylic acid or hydroxyl sulfoacid or their salt, sulphite etc., handle prepared leather tanning agent of modified aminoresin with amino hydroxy acid or thionamic acid or their salt and only improved water-soluble and stable (Zhou Hualong volume, the leather chemical industry material, China Light Industry Press, 2001); Publication number is that the Chinese patent application of CN 1544659 A mainly is to introduce the biphosphonate class formation group with good flame-retarding characteristic BMU is carried out modification, and prepared leather tanning agent of modified aminoresin can give leather good fire-retardant fireproof function.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, provide that a kind of free formaldehyde content is low, the leather tanning agent of modified aminoresin of good combination property and preparation method thereof.
Leather tanning agent of modified aminoresin of the present invention is formed by sulfonated amino resin and the condensation reaction of proteolytic degradation thing, the condensation reaction of sulfonated amino resin and proteolytic degradation thing schematically as follows:
In the above-mentioned reaction formula, R-NH-CH
2-OH is the schematic construction formula of sulfonated amino resin, NH
2-P is the schematic construction formula of proteolytic degradation thing, R-NH-CH
2-NH-P is the feature schematic construction formula of leather tanning agent of modified aminoresin of the present invention.
In the sulfonated amino resin residual free formaldehyde can with proteolytic degradation thing generation condensation reaction, thereby significantly reduce the content of free formaldehyde in the leather tanning agent of modified aminoresin, its reaction is as follows:
Leather tanning agent of modified aminoresin of the present invention both can be liquid, can be again the powder state.If liquid, wherein the content of leather tanning agent of modified aminoresin effective ingredient is 40～45% (mass percents).
The preparation method of leather tanning agent of modified aminoresin of the present invention, processing step comprises the condensation reaction of preparation, sulfonated amino resin and the proteolytic degradation thing of sulfonated amino resin.Concrete operations are as follows:
One, the preparation of liquid modified BMU
1, composition of raw materials
Raw material has following component, and the proportioning of each component is by mass parts,
100 parts in formaldehyde
50～100 parts of amino monomers
50～200 parts of sulphonating agents
25～200 parts of proteolytic degradation thing solution
50～200 parts of deionized waters
The mass concentration of described formaldehyde is 37～40%, and the mass concentration of described proteolytic degradation thing solution is 25%, viscosity is 500mPa.s～5000mPa.s.
2, processing step
(1) the formaldehyde adding is had in the reactor of agitator, thermometer and condenser, in room temperature, normal pressure with lye pH adjustment value to 8.5～10.5, be warming up to 70～95 ℃ then, under agitation add amino monomers and under 70～95 ℃ and agitation condition, reacted 30～90 minutes;
(2) 70～95 ℃ with lye pH adjustment value to 10.0～11.5, add sulphonating agent, deionized water and under 70～95 ℃ and agitation condition, reacted 60～120 minutes;
(3) be cooled to 60～65 ℃,, under 60～65 ℃ and agitation condition, reacted 60～180 minutes with acid solution adjust pH to 4.5～5.5;
(4) be cooled to 45～55 ℃, add proteolytic degradation thing solution and under agitation condition, reacted 60～180 minutes, with lye pH adjustment value to 6.5～7.5, promptly obtain liquid modified BMU then.
Two, the preparation of powder shaped leather tanning agent of modified aminoresin
1, composition of raw materials
Raw material has following component, and the proportioning of each component is by mass parts,
100 parts in formaldehyde
50～100 parts of amino monomers
50～200 parts of sulphonating agents
25～200 parts of proteolytic degradation thing solution
50～200 parts of deionized waters
The mass concentration of described formaldehyde is 37～40%, and the mass concentration of described proteolytic degradation thing solution is 25%, viscosity is 500mPa.s～5000mPa.s.
2, processing step
(1) the formaldehyde adding is had in the reactor of agitator, thermometer and condenser, in room temperature, normal pressure with lye pH adjustment value to 8.5～10.5, be warming up to 70～95 ℃ then, under agitation add amino monomers and under 70～95 ℃ and agitation condition, reacted 30～90 minutes;
(2) 70～95 ℃ with lye pH adjustment value to 10.0～11.5, add sulphonating agent, deionized water and under 70～95 ℃ and agitation condition, reacted 60～120 minutes;
(3) be cooled to 60～65 ℃,, under 60～65 ℃ and agitation condition, reacted 60～180 minutes with acid solution adjust pH to 4.5～5.5;
(4) be cooled to 45～55 ℃, add proteolytic degradation thing solution and under agitation condition, reacted 60～180 minutes, with lye pH adjustment value to 6.5～7.5, promptly obtain liquid modified BMU then;
(5) with liquid modified BMU spraying drying, control material inlet temperature is 130～140 ℃ during spraying, and temperature out is 80～90 ℃, promptly obtains powdered modified BMU.
Among the above-mentioned preparation method, amino monomers can be selected urea or trimeric cyanamide or Dyhard RU 100 for use, also 2 kinds of these amino monomers or 3 kinds composite, sulphonating agent is selected Sodium Metabisulfite or sodium bisulfite for use, the proteolytic degradation thing is animal proteinum degradation product or vegetable-protein degradation product, or the mixing of two kinds of proteolytic degradation things.The animal proteinum degradation product is selected collagen protein degradation product or keratin degrading thing or casein degradation product for use; The vegetable-protein degradation product is selected soybean protein degradation product or Semen arachidis hypogaeae protein degradation product or zein degradation product for use.
Among the above-mentioned preparation method, the used alkali lye of adjust pH is ammoniacal liquor or potassium hydroxide solution or sodium hydroxide solution or sodium carbonate solution, and acid solution is hydrochloric acid soln or sulphuric acid soln or acetum or formic acid solution.
When composition of raw materials designs, the mass concentration of proteolytic degradation thing solution both can be greater than 25%, also can be less than 25%, but variation along with proteolytic degradation thing solution quality concentration, the mass parts of proteolytic degradation thing solution must be done corresponding adjustment, the principle of adjusting is when adding the proteolytic degradation thing solution of other concentration, and the proteolytic degradation thing content in its mass fraction should be identical with the proteolytic degradation thing content in the proteolytic degradation thing solution quality umber of mass concentration 25%.For example, when the mass concentration of proteolytic degradation thing solution is 50%, then the mass fraction of proteolytic degradation thing solution should be adjusted into 12.5～100 parts.
The present invention has following beneficial effect:
1, leather tanning agent of modified aminoresin of the present invention has excellent comprehensive performances, relatively the seeing the following form of performance index such as its fillibility, plumpness, flexibility, water-absorbent, grain compactibility and conventional BMU:
| Fillibility | Plumpness | Flexibility | Water-absorbent | The grain compactibility | |
| Conventional BMU | ++++ | +++ | +++ | ++++ | ++++ |
| Leather tanning agent of modified aminoresin of the present invention | +++++ | +++++ | +++++ | +++ | ++++ |
Performance index are veteran process hides slip-stick artist's sensory evaluation in the last table, and wherein "+" is many more, illustrate that this performance is good more.As can be seen from the table, with respect to conventional BMU, its fillibility, plumpness, flexibility, grain compactibility improve, and water-absorbent reduces.
2, leather tanning agent of modified aminoresin of the present invention is applied in leather industry, the finished leather of being produced had both had advantages such as the original selection fillibility of common aminoresin, grain consolidation, has the protein filling filling properties again, make leather suppleness can be improved significantly, because it is same or similar that natural animal and plant albumen that uses and leather fiber are formed, so the consistency of leather tanning agent of modified aminoresin and leather is better.
3, leather tanning agent of modified aminoresin of the present invention; its free formaldehyde content＜0.3% (mass percent); minimum 0.03% (mass percent) (measuring method is with reference to GB 5544-85) that reach; this BMU is applied in the process hides; the finished leather formaldehyde content of being produced is not higher than 10mg/kg, and (measuring method is compiled " leather physico-chemical analysis " with reference to Jiang Weiqi, Gong Dezhen; light industry press 1987:347), helps the healthy of environment protection and operator.
4, the preparation method is simple, and raw material is easy to obtain, and is convenient to suitability for industrialized production.
Embodiment
Embodiment one
1, the preparation of proteolytic degradation thing
Raw material is the degreasing pigskin, and it is fully clean with tap water, takes by weighing 200g, add deionized water 200g, the sodium hydroxide solution adjust pH to 7.5 in room temperature, normal pressure usefulness mass concentration 10% adds 1398 proteolytic enzyme 50u/g skins, handled 1 hour down, wash 5 times with deionized water then for 40 ℃.In the degreasing pigskin after enzyme is handled, add deionized water 500g, be warming up to 80 ℃, insulated and stirred 2 hours is cooled to room temperature, obtains collagen protein degradation product liquid after the filtration, is concentrated into mass concentration 25%, viscosimetric 4g00mPa.s.
2, the preparation of liquid modified BMU
Composition of raw materials is as follows:
Raw material has following component, and the proportioning of each component is by mass parts,
100 parts in formaldehyde
50 parts in urea
50 parts of Sodium Metabisulfites
25 parts of collagen protein degradation product solution
50 parts of deionized waters
Described formaldehyde is industrial formol, and mass concentration is 37～40%, and the mass concentration of described collagen protein degradation product solution is 25%, viscosity is 4800mPa.s.
Processing step is as follows
(1) the formaldehyde adding is had in the reactor of agitator, thermometer and condenser, at room temperature, normal pressure mass concentration 25% sodium hydroxide solution adjust pH to 8.5, be warming up to 75 ℃ then, under agitation add urea and reaction 90 minutes under 75 ℃ and agitation condition;
(2) 75 ℃ with mass concentration 25% sodium hydroxide solution adjust pH to 10.0, add the reaction 120 minutes under 75 ℃ and agitation condition of Sodium Metabisulfite, deionized water;
(3) be cooled to 60 ℃, with mass concentration 25% hydrochloric acid soln adjust pH to 5.0, reaction is 150 minutes under 60 ℃ and agitation condition;
(4) be cooled to 45 ℃, add collagen protein degradation product solution and under agitation condition, reacted 60 minutes, use mass concentration 25% sodium hydroxide solution adjust pH to 6.5 then, promptly obtain liquid modified BMU.
In the leather tanning agent of modified aminoresin in the present embodiment, free formaldehyde content 0.25%.
Embodiment two
1, the preparation of proteolytic degradation thing
Get the 100g soybean protein isolate, add the 200g deionized water and regulate pH value to 8.0 with mass concentration 25% potassium hydroxide solution, be warming up to 55 ℃, add 1398 proteolytic enzyme 4g at room temperature, normal pressure, hydrolysis 1 hour, add mass concentration 25% hydrochloric acid soln adjust pH to 4.5, be heated to 80 ℃, insulated and stirred degraded 2 hours, isolate clear liquid after the cooling, be concentrated into mass concentration 25%, promptly obtain the soybean protein degradation product, viscosimetric 500mPa.s.
2, the preparation of liquid modified BMU
Composition of raw materials is as follows:
Raw material has following component, and the proportioning of each component is by mass parts,
100 parts in formaldehyde
60 parts of Dyhard RU 100s
100 parts of sodium bisulfites
120 parts of soybean protein degradation product solution
60 parts of collagen protein degradation product solution
80 parts of deionized waters
Described formaldehyde is industrial formol, mass concentration is 37～40%, the mass concentration of described soybean protein degradation product solution is 25%, viscosity is 500mPa.s, and the mass concentration of described collagen protein degradation product solution is 25%, viscosity is 4800mPa.s, with embodiment one described method preparation.
Processing step is as follows
(1) the formaldehyde adding is had in the reactor of agitator, thermometer and condenser, at room temperature, normal pressure mass concentration 25% potassium hydroxide solution adjust pH to 9.5, be warming up to 85 ℃ then, under agitation add Dyhard RU 100 and reaction 45 minutes under 85 ℃ and agitation condition;
(2) 85 ℃ with mass concentration 25% potassium hydroxide solution adjust pH to 11.0, add the reaction 60 minutes under 85 ℃ and agitation condition of sodium bisulfite, deionized water;
(3) be cooled to 65 ℃, with mass concentration 25% sulphuric acid soln adjust pH to 4.5, reaction is 60 minutes under 65 ℃ and agitation condition;
(4) be cooled to 50 ℃, add proteolytic degradation thing solution and under agitation condition, reacted 100 minutes, use mass concentration 25% potassium hydroxide solution adjust pH to 7.5 then, promptly obtain liquid modified BMU.
In the leather tanning agent of modified aminoresin in the present embodiment, free formaldehyde content 0.18%
Embodiment three
1, the preparation of proteolytic degradation thing
Take by weighing the 200g casein, add the 200g distilled water and the 6g vitriol oil at room temperature, normal pressure, be warming up to 75 ℃ under stirring, hydrolysis reaction 5 hours, use mass concentration 20% sodium hydroxide solution adjust pH to 7.0 then, get upper strata collagen hydrolyzed solution after the layering, be concentrated into mass concentration 25%, promptly obtain the casein degradation product, viscosimetric 800mPa.s.
2, the preparation of liquid modified BMU
Composition of raw materials is as follows:
Raw material has following component, and the proportioning of each component is by mass parts,
100 parts in formaldehyde
70 parts of trimeric cyanamides
100 parts of sodium bisulfites
150 parts of casein degradation product solution
110 parts of deionized waters
Described formaldehyde is industrial formol, and mass concentration is 37～40%, and the mass concentration of described casein degradation product solution is 25%, viscosity is 800mPa.s.
Processing step is as follows
(1) formaldehyde is added has in the reactor of agitator, thermometer and condenser, with ammoniacal liquor adjust pH to 10.0, be warming up to 90 ℃ then, under agitation add trimeric cyanamide and reaction 50 minutes under 90 ℃ and agitation condition at room temperature, normal pressure;
(2) 90 ℃ with ammoniacal liquor adjust pH to 11.5, add the reaction 80 minutes under 90 ℃ and agitation condition of sodium bisulfite, deionized water;
(3) be cooled to 65 ℃, with mass concentration 25% acetum adjust pH to 5.5, reaction is 90 minutes under 65 ℃ and agitation condition;
(4) be cooled to 55 ℃, add casein degradation product solution and under agitation condition, reacted 120 minutes, use ammoniacal liquor adjust pH to 7.5 then, promptly obtain liquid modified BMU.
Leather tanning agent of modified aminoresin in the present embodiment, free formaldehyde content 0.18%.
Embodiment four
1, the preparation of proteolytic degradation thing
Raw material is the blue leather bits of ox-hide shaving.The blue leather of shaving crumb tap water is fully clean, take by weighing 200g, add deionized water 200g, with 25% sodium hydroxide solution adjust pH to 10.5～11.0,2709 proteolytic enzyme consumption 200u/g (the blue leather bits of shaving meter) handled 1 hour down, are warming up to 90～95 ℃ for 50 ℃, add lime powder 7%, insulated and stirred 2 hours, cooling is filtered, and collagen protein degradation product solution is neutralized to pH value 7.0～7.5 with mass concentration 15% hydrochloric acid soln, be concentrated into concentration 25%, viscosimetric 1500mPa.s.
2, the preparation of powdered modified BMU
Composition of raw materials is as follows:
Raw material has following component, and the proportioning of each component is by mass parts,
100 parts in formaldehyde
40 parts in urea
40 parts of trimeric cyanamides
120 parts of Sodium Metabisulfites
60 parts of collagen protein degradation product solution
150 parts of deionized waters
Described formaldehyde is industrial formol, and mass concentration is 37～40%, and the mass concentration of described collagen protein degradation product solution is 25%, viscosity is 1500mPa.s.
Processing step is as follows
(1) the formaldehyde adding is had in the reactor of agitator, thermometer and condenser, at room temperature, normal pressure mass concentration 25% sodium hydroxide solution adjust pH to 9.5, be warming up to 95 ℃ then, under agitation add urea, trimeric cyanamide and reaction 45 minutes under 95 ℃ and agitation condition;
(2) 95 ℃ with mass concentration 25% sodium hydroxide solution adjust pH to 11.0, add the reaction 60 minutes under 95 ℃ and agitation condition of Sodium Metabisulfite, deionized water;
(3) be cooled to 60 ℃, with mass concentration 25% formic acid solution adjust pH to 4.5, reaction is 120 minutes under 60 ℃ and agitation condition;
(4) be cooled to 50 ℃, add collagen protein degradation product solution and under agitation condition, reacted 90 minutes, use mass concentration 25% sodium hydroxide solution adjust pH to 7.0 then, promptly obtain liquid modified BMU.
(5) liquid product that obtains is carried out spraying drying, control material inlet temperature is 130 ℃ during spraying, and temperature out is 80 ℃, promptly obtains powdered modified BMU.
Leather tanning agent of modified aminoresin in the present embodiment, free formaldehyde content 0.07%.
Embodiment five
1, the preparation of proteolytic degradation thing
Raw material is a peanut protein isolate, it is fully clean with tap water, take by weighing 200g, add deionized water 200g, use the sodium hydroxide solution adjust pH to 7.5 of mass concentration 25% at room temperature, normal pressure, add 1398 proteolytic enzyme 50u/g peanut protein isolates, handled 1 hour down, wash 5 times with deionized water then for 40 ℃.Add deionized water 500g, be warming up to 80 ℃, insulated and stirred 2 hours is cooled to room temperature, obtains Semen arachidis hypogaeae protein degradation product liquid after the filtration, is concentrated into mass concentration 25%, viscosimetric 2000mPa.s.
2, the preparation of powdered modified BMU
Composition of raw materials is as follows:
Raw material has following component, and the proportioning of each component is by mass parts,
100 parts in formaldehyde
30 parts in urea
55 parts of trimeric cyanamides
180 parts of Sodium Metabisulfites
100 parts of Semen arachidis hypogaeae protein degradation product solution
100 parts of deionized waters
Described formaldehyde is industrial formol, and mass concentration is 37～40%, and the mass concentration of described Semen arachidis hypogaeae protein degradation product solution is 25%, viscosity is 2000mPa.s.
Processing step is as follows
(1) the formaldehyde adding is had in the reactor of agitator, thermometer and condenser, at room temperature, normal pressure mass concentration 25% sodium carbonate solution adjust pH to 10.0, be warming up to 85 ℃ then, under agitation add urea, trimeric cyanamide and reaction 30 minutes under 85 ℃ and agitation condition;
(2) 85 ℃ with mass concentration 25% sodium carbonate solution adjust pH to 10.5, add the reaction 90 minutes under 85 ℃ and agitation condition of Sodium Metabisulfite, deionized water;
(3) be cooled to 60 ℃, with mass concentration 25% hydrochloric acid soln adjust pH to 5.0, reaction is 120 minutes under 60 ℃ and agitation condition;
(4) be cooled to 55 ℃, add Semen arachidis hypogaeae protein degradation product solution and under agitation condition, reacted 60 minutes, use mass concentration 25% sodium carbonate solution adjust pH to 6.5 then, promptly obtain liquid modified BMU.
(5) liquid product that obtains is carried out spraying drying, control material inlet temperature is 135 ℃ during spraying, and temperature out is 85 ℃, promptly obtains powdered modified BMU.
Leather tanning agent of modified aminoresin in the present embodiment, free formaldehyde content 0.12%.
Embodiment six
1, the preparation of proteolytic degradation thing
Raw material is a chicken feather, and chicken feather powder is broken into powder, takes by weighing 200g, adds 500g 4% sodium hydroxide solution at room temperature, normal pressure, is warming up to 70 ℃, and insulated and stirred hydrolysis 4 hours is cooled to room temperature, leaves standstill, and filters.Filtrate under agitation is neutralized to pH value 7.0～7.5 with concentrated hydrochloric acid, obtains keratin degrading thing liquid, is concentrated into mass concentration 25%, viscosimetric 3500mPa.s.
2, the preparation of powdered modified BMU
Composition of raw materials is as follows:
Raw material has following component, and the proportioning of each component is by mass parts,
100 parts in formaldehyde
25 parts in urea
50 parts of trimeric cyanamides
25 parts of Dyhard RU 100s
70 parts of Sodium Metabisulfites
140 parts of keratin degrading thing solution
60 parts of Semen arachidis hypogaeae protein degradation product solution
200 parts of deionized waters
Described formaldehyde is industrial formol, mass concentration is 37～40%, the mass concentration of described keratin degrading thing solution is 25%, viscosity is 3500mPa.s, and the mass concentration of described Semen arachidis hypogaeae protein degradation product solution is 25%, viscosity is 2000mPa.s, with embodiment five described methods preparations.
Processing step is as follows
(1) the formaldehyde adding is had in the reactor of agitator, thermometer and condenser, at room temperature, normal pressure mass concentration 25% sodium hydroxide solution adjust pH to 9.5, be warming up to 80 ℃ then, under agitation add urea, trimeric cyanamide and reaction 90 minutes under 80 ℃ and agitation condition;
(2) 80 ℃ with mass concentration 25% sodium hydroxide solution adjust pH to 10.5, add the reaction 120 minutes under 80 ℃ and agitation condition of Sodium Metabisulfite, deionized water;
(3) be cooled to 65 ℃, with mass concentration 25% acetum adjust pH to 5.5, reaction is 120 minutes under 65 ℃ and agitation condition;
(4) be cooled to 45 ℃, add proteolytic degradation thing solution and under agitation condition, reacted 180 minutes, use mass concentration 25% sodium hydroxide solution adjust pH to 6.5 then, promptly obtain liquid modified BMU.
(5) liquid product that obtains is carried out spraying drying, control material inlet temperature is 140 ℃ during spraying, and temperature out is 90 ℃, promptly obtains powdered modified BMU.
Leather tanning agent of modified aminoresin in the present embodiment, free formaldehyde content 0.03%.
Claims (9)
1, a kind of leather tanning agent of modified aminoresin, it is characterized in that forming by sulfonated amino resin and the condensation reaction of proteolytic degradation thing, processing step is: (1) adds formaldehyde and has in the reactor of agitator, thermometer and condenser, in room temperature, normal pressure with lye pH adjustment value to 8.5～10.5, be warming up to 70～95 ℃ then, under agitation add amino monomers and under 70～95 ℃ and agitation condition, reacted 30～90 minutes; (2) 70～95 ℃ with lye pH adjustment value to 10.0～11.5, add sulphonating agent, deionized water and under 70～95 ℃ and agitation condition, reacted 60～120 minutes; (3) be cooled to 60～65 ℃,, under 60～65 ℃ and agitation condition, reacted 60～180 minutes with acid solution adjust pH to 4.5～5.5; (4) be cooled to 45～55 ℃, add proteolytic degradation thing solution and under agitation condition, reacted 60～180 minutes, then with lye pH adjustment value to 6.5～7.5; This leather tanning agent of modified aminoresin has following feature schematic construction formula:
R-NH-CH
2-NH-P
In the above-mentioned schematic construction formula, R is the sulfonated amino resin residue, and P is a proteolytic degradation thing residue.
2, leather tanning agent of modified aminoresin according to claim 1 is characterized in that form is liquid, and wherein the mass percent of leather tanning agent of modified aminoresin effective ingredient is 40～45%.
3, leather tanning agent of modified aminoresin according to claim 1 is characterized in that form is powdery.
4, the preparation method of the described leather tanning agent of modified aminoresin of a kind of claim 2 is characterized in that:
I. composition of raw materials
Raw material has following component, and the proportioning of each component is by mass parts,
100 parts in formaldehyde
50～100 parts of amino monomers
50～200 parts of sulphonating agents
25～200 parts of proteolytic degradation thing solution
50～200 parts of deionized waters
The mass concentration of described formaldehyde is 37～40%, and the mass concentration of described proteolytic degradation thing solution is 25%, viscosity is 500mPa.s～5000mPa.s;
II. processing step
(1) the formaldehyde adding is had in the reactor of agitator, thermometer and condenser, in room temperature, normal pressure with lye pH adjustment value to 8.5～10.5, be warming up to 70～95 ℃ then, under agitation add amino monomers and under 70～95 ℃ and agitation condition, reacted 30～90 minutes;
(2) 70～95 ℃ with lye pH adjustment value to 10.0～11.5, add sulphonating agent, deionized water and under 70～95 ℃ and agitation condition, reacted 60～120 minutes;
(3) be cooled to 60～65 ℃,, under 60～65 ℃ and agitation condition, reacted 60～180 minutes with acid solution adjust pH to 4.5～5.5;
(4) be cooled to 45～55 ℃, add proteolytic degradation thing solution and under agitation condition, reacted 60～180 minutes, with lye pH adjustment value to 6.5～7.5, promptly obtain liquid modified BMU then.
5, the preparation method of the described leather tanning agent of modified aminoresin of a kind of claim 3 is characterized in that composition of raw materials is described component of claim 4 and proportioning, and processing step is to increase the spraying drying step afterwards at the described processing step of claim 4 (4).
6,, it is characterized in that the proteolytic degradation thing is that the animal proteinum degradation product is or/and the vegetable-protein degradation product according to the preparation method of claim 4 or 5 described leather tanning agent of modified aminoresin.
7, the preparation method of leather tanning agent of modified aminoresin according to claim 6 is characterized in that the animal proteinum degradation product is collagen protein degradation product or keratin degrading thing or casein degradation product.
8, the preparation method of leather tanning agent of modified aminoresin according to claim 6 is characterized in that the vegetable-protein degradation product is soybean protein degradation product or Semen arachidis hypogaeae protein degradation product or zein degradation product.
9,, it is characterized in that sulphonating agent is Sodium Metabisulfite or sodium bisulfite according to the preparation method of claim 4 or 5 described leather tanning agent of modified aminoresin.
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| CN107385124B (en) * | 2017-08-02 | 2019-09-17 | 兴业皮革科技股份有限公司 | A kind of method that organic phosphine and chitin modified keratin prepare Techniques of Protein Filling Agents |
| CN109136424A (en) * | 2018-08-13 | 2019-01-04 | 淄博环亚助剂科技有限公司 | A kind of no aldehyde leather agent and preparation method |
| EP4229134A1 (en) * | 2020-10-15 | 2023-08-23 | Université Jean Monnet Saint-Étienne | Biobased material and method for preparing same |
| CN112626291B (en) * | 2020-12-31 | 2022-03-18 | 中国皮革制鞋研究院有限公司 | Bio-based amino resin retanning agent and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5749682A (en) * | 1980-09-09 | 1982-03-23 | Sugiyama Sangyo Kagaku Kenkyusho | Water-resistant adhesive |
| US4942191A (en) * | 1988-04-25 | 1990-07-17 | Borden, Inc. | Aldehyde condensation resin glue compositions having pea and other leguminous flour extenders |
| CN1544659A (en) * | 2003-11-26 | 2004-11-10 | 四川大学 | Leather flame-retardant amino resin tanning agent and its preparation method |
-
2005
- 2005-06-02 CN CNB2005100210212A patent/CN1317396C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5749682A (en) * | 1980-09-09 | 1982-03-23 | Sugiyama Sangyo Kagaku Kenkyusho | Water-resistant adhesive |
| US4942191A (en) * | 1988-04-25 | 1990-07-17 | Borden, Inc. | Aldehyde condensation resin glue compositions having pea and other leguminous flour extenders |
| CN1544659A (en) * | 2003-11-26 | 2004-11-10 | 四川大学 | Leather flame-retardant amino resin tanning agent and its preparation method |
Non-Patent Citations (1)
| Title |
|---|
| 新型改性氨基树脂鞣剂的合成工艺 李立新，中国皮革，第33卷第1期 2004 * |
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| CN1687463A (en) | 2005-10-26 |
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