CN100387728C - Composite phosphate grease-adding agent for leather and its preparation method - Google Patents

Composite phosphate grease-adding agent for leather and its preparation method Download PDF

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CN100387728C
CN100387728C CNB2006100506466A CN200610050646A CN100387728C CN 100387728 C CN100387728 C CN 100387728C CN B2006100506466 A CNB2006100506466 A CN B2006100506466A CN 200610050646 A CN200610050646 A CN 200610050646A CN 100387728 C CN100387728 C CN 100387728C
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leather
oil
composite
amidation
preparation
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CN1865454A (en
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兰云军
鲍利红
罗卫平
董贵平
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Wenzhou University
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Wenzhou University
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Abstract

The present invention provides a composite phosphate leather greasing agent and a preparation method thereof. The composite phosphate leather greasing agent contains phosphorylated vegetable oil, soybean lecithin, alkyl sulfonamide special for leather and Syn amphoteric synthetic greasing material. The preparation method comprises the steps that vegetable oil and ethanolamine react to obtain amidated vegetable oil; then the phosphorylation is carried out by P2O5 dispersed by a composite dispersing agent; a certain quantity of oil-soluble emulsifying agent is added when the phosphorylation is carried out; the mixture is hydrolyzed to obtain the phosphorylated vegetable oil after the phosphorylation is finished; then soybean lecithin, alkyl sulfonamide special for leather and Syn amphoteric synthetic greasing material are added to the phosphorylated vegetable oil to prepare the composite phosphate leather greasing agent by the neutralization and the regulation of the contents of effective substances. The composite phosphate leather greasing agent of the present invention does not contain APEO and chloroparaffin limited by the European Union and has the advantages of good appearance, high stability when stored at low temperature, strong capability for resisting dielectric, and the leather greased by the composite phosphate leather greasing agent has the advantages of good softness, moisture leather surface, good light resistance and good greasing effect, and furthermore, the greasing effect can be kept for a long time.

Description

A kind of composite phosphate grease-adding agent for leather and preparation method thereof
Technical field
The invention belongs to the leather chemical industry technical field, particularly relate to a kind of compound leather fat of phosphate vegetable oil and preparation method thereof that contains.
Background technology
Fatting agent is the skin material of consumption maximum in the tanning production, also is one of important chemical materials in the leather processing procedure.It can lubricate leather fiber, prevents stiff, the cracking of leather, can make leather have corresponding toughness and flexibility again, and keep its intensity, and it is the important factor that influences the leather quality performance.The phosphoric acid ester fatting agent has become the exploitation focus of novel fatting agent because of its excellent performance in recent years.The phosphate radical active group that contains in this class fatting agent molecular structure can enter the amino effect of removing from office together in the leather on the fiber, forms complex body with protein, thereby has stuffing and filling effect; In addition, the chromium in phosphate radical functional group and the leather has very strong complexing, by means of this complexing, leather is produced " permanent " stuffing effect, makes leather keep soft, plentiful, flexible for a long time, and has certain mercerising sense, wax sense and moisten feel.The phosphate fat-liquoring agent good penetrability is handled leather and is had excellent hydrophobic property and mercerising performance, this has been carried out a large amount of research in recent years both at home and abroad.In addition, there is research report phosphoric acid ester volatility low, good stability, nonflammable, can give the leather flame retardant resistance.And phosphoric acid ester is easy to biological degradation, under photochemical catalysis, resolves into CO 2And phosphate anion, toxicity is very little, can not pollute in producing and using.Therefore, synthetic phosphoric acid ester is a kind of comparatively ideal stuffing material, and the quality that improves finished leather is had positive effect.
But this type of domestic production fatting agent is a basic raw material with aliphatic hydrocarbon, alicyclic hydrocarbon, fluorine fat hydrocarbon and derivative thereof mainly at present, though all have certain stuffing effect, but exist the operational path complexity, the production cycle is long, and the synthetic technology difficulty is bigger, production unit is required high, the material price height, biological degradability is poor, and performance is single, have shortcomings such as gap with external like product, the domestic market of this type of expensive goods is captured by offshore company for a long time.Therefore, exploitation composite phosphate fatting agent high-grade, environmental protection has great importance for improving China's fatting agent product specification and taking part in international competition.
Summary of the invention
The purpose of this invention is to provide a kind of composite phosphate grease-adding agent for leather and preparation method thereof, this composite phosphate grease-adding agent for leather contains multiple component with different stuffing performances, comprehensive stuffing performance is good, its preparation method is simple relatively, less demanding to production unit, the production cycle is also shorter.
The technical solution used in the present invention is:
A kind of composite phosphate grease-adding agent for leather contains phosphorylation amidation vegetables oil, the special-purpose alkyl sulfonamide of leather and soybean lecithin, also contains the synthetic stuffing material of Syn both sexes; The ratio of each component is: phosphorylation amidation vegetables oil 40%~50%, stuffing material 20%~30% is synthesized in the Syn both sexes, the special-purpose alkyl sulfonamide 20%~25% of leather, soybean lecithin 5%~10%.
In the above-mentioned composite phosphate grease-adding agent for leather, described phosphorylation amidation vegetables oil, is used in the presence of oil-soluble emulsifier and is adopted composite dispersing agent dispersive P after the Monoethanolamine MEA BASF amidation by vegetables oil 2O 5Phosphorylation obtains through hydrolysis again.
The preparation method of described a kind of composite phosphate grease-adding agent for leather comprises amidation, phosphorylation, hydrolysis and composite step:
(1) amidation: with Monoethanolamine MEA BASF vegetables oil is carried out the amidation modification, described vegetables oil is rapeseed oil, plam oil or soybean oil, or the mixture of rapeseed oil, plam oil and soybean oil three arbitrary proportion; The mass ratio of described vegetables oil and Monoethanolamine MEA BASF is 100: 6~11, be preferably 100: 7~and 10; Temperature of reaction is 120 ℃~150 ℃, is preferably 130 ℃~145 ℃; Under the catalyst-free condition, react 2.0h~3.0h; React the amidation vegetables oil, reaction finishes the hydroxyl value that the amidation vegetables oil is measured in the back.
(2) phosphorylation: after the amidation vegetables oil that described step (1) is obtained is cooled to about 70 ℃, add oil-soluble emulsifier; Described oil-soluble emulsifier is selected the Span series of surfactants for use, preferred Span80, and the consumption of Span80 is 1%~10% of an amidation vegetables oil, is preferably 2%~7%, the best is 3%~5%;
Selecting the composite inert oil plant then for use is composite dispersing agent, described composite inert oil plant is made up of the chlorination rape oil fatty acid methyl esters and the white oil of chlorinity 20%, its mass ratio is: the chlorination rape oil fatty acid methyl esters of chlorinity 20%: white oil=2.0~4.0: 1.0, be preferably 2.5~3.5: 1.0; With adopting described composite inert oil plant dispersive P 2O 5Phosphorylation, P 2O 5With the mass ratio of composite inert oil plant be 1.0: 1.0~2.0, be preferably 1.0: 1.4~1.8; Described employing composite inert oil plant dispersive P 2O 5Add-on be: amidation vegetables oil hydroxyl and Span80 hydroxyl sum and P 2O 5Mol ratio be 1.0: 0.35~0.5, be preferably 1.0: 0.4~0.48;
Temperature of reaction is 60 ℃~90 ℃, is preferably 65 ℃~85 ℃, and the best is 70 ℃~85 ℃, and the reaction times is 2.0h~3.0h.
(3) hydrolysis: in described step (2) products therefrom, add a spot of water, add the amount and the P of entry 2O 5Mol ratio be 1.5~2.0: 1.0, promptly obtain phosphorylation amidation vegetables oil, be called for short phosphate vegetable oil.
(4) composite: the phosphorylation amidation vegetables oil that described step (3) is obtained is cooled to 50~60 ℃, adds the synthetic stuffing material of Syn both sexes, the special-purpose alkyl sulfonamide of leather and soybean lecithin; The ratio of each component is a phosphorylation amidation vegetables oil 40%~50%, and stuffing material 20%~30% is synthesized in the Syn both sexes, the special-purpose alkyl sulfonamide 20%~25% of leather, soybean lecithin 5%~10%; Composite temperature is 40 ℃~70 ℃, is preferably 50 ℃~65 ℃; Mix the aqueous sodium hydroxide solution neutralization of back adding 30%, the pH value of regulation system is 6.0~8.0 simultaneously; Then in system, add a certain amount of water again, regulate working substance content 〉=70% of product; Continue to stir 0.5h~2.0h, be preferably 1.0h~1.5h, promptly obtain the final product composite phosphate grease-adding agent for leather.
Among the preparation method of above-mentioned composite phosphate grease-adding agent for leather, described white oil is No. 5 white oils, No. 10 white oils or No. 15 white oils.
Composite phosphate grease-adding agent for leather product among the present invention comprises phosphorylation amidation vegetables oil, soybean lecithin, the special-purpose alkyl sulfonamide of leather and the synthetic stuffing material of Syn both sexes, wherein phosphorylation amidation vegetables oil is a kind of intermediate of preparation method's synthetic by the composite phosphate grease-adding agent for leather among the present invention, to wherein introducing soybean lecithin, the special-purpose alkyl sulfonamide of leather and the synthetic stuffing material of Syn both sexes, finally obtain the good composite phosphate grease-adding agent for leather of stability, low tempertaure storage and fat added then.Its preparation flow as shown in drawings.
Chemical reaction mechanism of the present invention is as follows:
The synthesis mechanism of phosphorylation amidation vegetables oil:
The amidate action of the first step vegetables oil
Wherein: m 1+ m 2+ m 3=m, m 1+ 2m 2+ 3m 3=n; When n≤1, m 2=m 3=0; When 1<n≤2, m 3=0.
The second step phosphorylation reaction
Wherein: DAP represents phosphorylation amidation vegetables oil dibasic acid esters, and MAP represents phosphorylation amidation vegetables oil monoesters.
The reaction of the 3rd one-step hydrolysis
The preparation method of the composite phosphate grease-adding agent for leather among the present invention is: adopt Monoethanolamine MEA BASF that vegetables oil is carried out amidation earlier, obtain the amidation vegetables oil; Adopt P then 2O 5It is carried out phosphorylation, in the amidation vegetables oil, add a certain amount of oil-soluble emulsifier, phosphorylation agent P during phosphorylation 2O 5Feed intake after adopting composite dispersing agent to disperse; After phosphorylation reaction is finished, in system, add a spot of water and be hydrolyzed, promptly obtain phosphorylation amidation vegetables oil.Adopt compounded technology in phosphorylation amidation vegetables oil, to introduce soybean lecithin, the special-purpose alkyl sulfonamide of leather and the synthetic stuffing material of Syn both sexes then, the pH value of sodium hydroxide regulation system with 30%, add a certain amount of water then and regulate working substance content, promptly obtain composite phosphate grease-adding agent for leather.
The employed amidation vegetables oil of preparation phosphorylation amidation vegetables oil is obtained by vegetables oil and Monoethanolamine MEA BASF reaction among the present invention.Vegetables oil can obtain the amidation vegetables oil of different hydroxyl values by amidation.Table 1 with the rapeseed oil be example provided rapeseed oil with different mass than and Monoethanolamine MEA BASF reaction, the hydroxyl value of the amidation rapeseed oil that records with the diacetyl oxide method.
Table 1 rapeseed oil and Monoethanolamine MEA BASF are with the hydroxyl value of different mass than the amidation rapeseed oil that makes
Preparation phosphorylation amidation vegetables oil employed oil-soluble emulsifier among the present invention requires in the molecular structure to contain hydroxyl and ester bond, is water-soluble behind phosphorylation reaction, can the increase system in the mutual solubility of different oil components, improve transparency of products.Special recommendation Span series of surfactants is preferably Span80.The hydroxyl value of Span80 is 190~250mgKOH/g.
When preparing phosphorylation amidation vegetables oil among the present invention, phosphorylation agent P 2O 5The employing dispersion method feeds intake, and the slowly-releasing reaction has fundamentally solved P 2O 5Directly feed intake can produce such as drawbacks such as caking, grease charing and appearance poor.Composite dispersing agent adopts the composite inert oil plant, can guarantee P 2O 5Scattered, the composite inert oil plant also has good mutual solubility with other component in the system simultaneously.
When preparing phosphorylation amidation vegetables oil among the present invention, regulate the consumption of phosphorylation agent according to the performance requriements of desired product.Phosphorylation amidation vegetables oil monoesters emulsifying property, good penetrability, the stuffing leather is soft; Phosphorylation amidation vegetables oil dibasic acid esters emulsifying property is relatively poor, but fillibility is good.According to above determined amidation vegetables oil hydroxyl and Span80 hydroxyl sum and P 2O 5The mole proportioning, will obtain stuffing leather performance softish based on the phosphorylation amidation vegetables oil of monoesters.
Among the present invention during preparation phosphorylation amidation vegetables oil, for guaranteeing polyphosphoric acid that its phosphorylation reaction generates by complete hydrolysis, the amount that adds entry should be higher than theoretical value, usually, adds the amount and the P of entry 2O 5Mol ratio be 1.5~2.0: 1.0.
The composite phosphate grease-adding agent for leather for preparing among the present invention is except containing phosphorylation amidation vegetables oil, also to wherein having introduced soybean lecithin, the special-purpose alkyl sulfonamide of leather and the synthetic stuffing material of Syn both sexes, to improve its stability and stuffing performance.Wherein needing ben is that the introducing of the synthetic stuffing material of Syn both sexes can increase the mutual solubility of system, muddiness when preventing to store, raising product winter (〉=2 ℃) transparency.
Composite phosphate grease-adding agent for leather outward appearance of the present invention is the transparent oily matter of reddish-brown, and the pH value is 6.0~8.0, working substance content 〉=70%, water miscible liquid 24h was not stratified in 1: 9, and no oil slick, product have good low-temp storage, haze-free more than 2 ℃, room temperature is deposited and was never degenerated in 6 months.
The preparation method who prepares the special-purpose alkyl sulfonamide of the used leather of composite phosphate grease-adding agent for leather among the present invention can show " preparation-theory and practice of leather chemicals " referring to doctor Lan Yunjun, and (China Light Industry Press publishes, 2001.1 version, the 93-94 page or leaf).
The required synthetic stuffing material of Syn both sexes of preparation composite phosphate grease-adding agent for leather is a proprietary material among the present invention, outward appearance is reddish brown transparent oily liquid, working substance content 〉=60%, the pH value is 6.0~9.0, produce (factory site: foundations of a house village, newly-built town, Jinyun, Zhejiang Province county by Jinyun, Zhejiang Province county leather agent factory, postcode: 321402, phone: 0578-3700560).
The used P of preparation phosphorylation amidation vegetables oil among the present invention 2O 5The chlorination rape oil fatty acid methyl esters component of chlorinity 20% is the special raw material for the special exploitation of the present invention in the composite dispersing agent, outward appearance is the reddish-brown oily liquids, chlorinity is 20% ± 2%, (factory site: No. 4, the road in Xinji City, Hebei province suffering by the deerskin hair welfare auxiliary reagent factory's production of Xinji City, Hebei province China, postcode: 052360, phone: 0311-88332142).
Composite phosphate grease-adding agent for leather of the present invention contains multiple component with different stuffing performances, and therefore comprehensive stuffing performance is good.Leather softness, leather surface with its stuffing moistens, photostabilization is good, the stuffing effect can keep for a long time.
Composite phosphate grease-adding agent for leather of the present invention does not contain the APEO (polyoxyethylene nonylphenol ether and polyoxyethylene octylphenol ether) and the clorafin of European Union's restriction, and basic three-waste free discharge belongs to environmentally friendly machine in production and the use.
Description of drawings
Accompanying drawing is preparation method's schema among the present invention.
Embodiment
Embodiment 1:
100.0g rapeseed oil and the adding of 7.0g Monoethanolamine MEA BASF are equipped with in the dry four-hole glass flask of agitator, prolong, are warming up to 135 ℃ and carry out amidate action, reaction is carried out obtaining the amidation rapeseed oil that hydroxyl value is 113.94mgKOH/g behind the 2.5h.In the amidation rapeseed oil, add 3.21g (amidation rapeseed oil heavy 3%) Span80, the amount of the total hydroxylated material of system this moment is 0.2292mol, slowly add then with the 21.87g composite dispersing agent (the chlorination rape oil fatty acid methyl esters of m[chlorinity 20%]: the m[5 white oil]=2.5: 1) P of dissolved 14.58g 2O 5(OH: P 2O 5[mol]=1: 0.45) phosphorylation, keeping temperature of reaction is 75 ℃, carries out 2.0h.Add 2.78g water (H then 2O: P 2O 5[mol]=1.5: 1) hydrolysis, promptly obtain phosphorylation amidation rapeseed oil.System is cooled to 55 ℃ then, to wherein adding the special-purpose alkyl sulfonamide of 59.77g leather, the synthetic stuffing material of 59.77g Syn both sexes and 29.90g soybean lecithin, stir the back to the sodium hydroxide solution neutralization that wherein drips 30%, the pH value of system is adjusted to about 7.0, be adjusted to working substance content 〉=70% to wherein adding 10g water then, after water injection, insulation continues to stir 1.0h, promptly obtains composite phosphate grease-adding agent for leather.
Embodiment 2:
100.0g plam oil and the adding of 8.0g Monoethanolamine MEA BASF are equipped with in the dry four-hole glass flask of agitator, prolong, are warming up to 140 ℃ and carry out amidate action, reaction is carried out obtaining the amidation plam oil that hydroxyl value is 129.01mgKOH/g behind the 2.5h.In the amidation plam oil, add 4.32g (amidation plam oil heavy 4%) Span80, the amount of the total hydroxylated material of system this moment is 0.2647mol, slowly add then with the 26.94g composite dispersing agent (the chlorination rape oil fatty acid methyl esters of m[chlorinity 20%]: the m[5 white oil]=2.5: 1) P of dissolved 16.84g 2O 5(OH: P 2O 5[mol]=1: 0.45) phosphorylation, keeping temperature of reaction is 75 ℃, carries out 2.0h.Add 3.43g water (H then 2O: P 2O 5[mol]=1.5: 1) hydrolysis, promptly obtain phosphorylation amidation plam oil.System is cooled to 60 ℃ then, to wherein adding the special-purpose alkyl sulfonamide of 63.81g leather, the synthetic stuffing material of 63.81g Syn both sexes and 31.90g soybean lecithin, stir the back to the sodium hydroxide solution neutralization that wherein drips 30%, the pH value of system is adjusted to about 7.0, be adjusted to working substance content 〉=70% to wherein adding 12g water then, after water injection, insulation continues to stir 1.0h, promptly obtains composite phosphate grease-adding agent for leather.
Embodiment 3:
100.0g rapeseed oil and the adding of 9.0g Monoethanolamine MEA BASF are equipped with in the dry four-hole glass flask of agitator, prolong, are warming up to 140 ℃ and carry out amidate action, reaction is carried out obtaining the amidation rapeseed oil that hydroxyl value is 143.81mgKOH/g behind the 2.5h.In the amidation rapeseed oil, add 4.36g (amidation rapeseed oil heavy 4%) Span80, the amount of the total hydroxylated material of system this moment is 0.2964mol, slowly add then with the 31.52g composite dispersing agent (the chlorination rape oil fatty acid methyl esters of m[chlorinity 20%]: the m[10 white oil]=2.5: 1) P of dissolved 19.70g 2O 5(OH: P 2O 5[mol]=1: 0.47) phosphorylation, keeping temperature of reaction is 80 ℃, carries out 2.0h.Add 4.51g water (H 2O: P then 2O 5[mol]=1.8: 1) hydrolysis, promptly obtain phosphorylation amidation rapeseed oil.System is cooled to 55 ℃ then, to wherein adding the special-purpose alkyl sulfonamide of 93.93g leather, 93.93g synthetic stuffing material of Syn both sexes and 19.78g soybean lecithin, stir the back to the sodium hydroxide solution neutralization that wherein drips 30%, the pH value of system is adjusted to about 7.0, is adjusted to working substance content 〉=70% to wherein adding 7g water then, after water injection after, insulation continues to stir 1.0h, promptly obtains composite phosphate grease-adding agent for leather.
Embodiment 4:
70.0g rapeseed oil, 30.0g soybean oil and the adding of 10.0g Monoethanolamine MEA BASF are equipped with in the dry four-hole glass flask of agitator, prolong, be warming up to 140 ℃ and carry out amidate action, reaction is carried out obtaining the amidation vegetables oil that hydroxyl value is 158.34mgKOH/g behind the 3.0h.In the amidation vegetables oil, add 5.50g (amidation vegetables oil heavy 5%) Span80, the amount of the total hydroxylated material of system this moment is 0.3319mol, slowly add then with the 36.70g composite dispersing agent (the chlorination rape oil fatty acid methyl esters of m[chlorinity 20%]: the m[5 white oil]=2.5: 1) P of dissolved 21.59g 2O 5(OH: P 2O 5[mol]=1: 0.46) phosphorylation, keeping temperature of reaction is 80 ℃, carries out 2.0h.Add 4.95g water (H then 2O: P 2O 5[mol]=1.5: 1) hydrolysis, promptly obtain phosphorylation amidation vegetables oil.System is cooled to 55 ℃ then, to wherein adding the special-purpose alkyl sulfonamide of 79.44g leather, the synthetic stuffing material of 99.3g Syn both sexes and 39.72g soybean lecithin, stir the back to the sodium hydroxide solution neutralization that wherein drips 30%, the pH value of system is adjusted to about 7.0, be adjusted to working substance content 〉=70% to wherein adding 17g water then, after water injection, insulation continues to stir 1.0h, promptly obtains composite phosphate grease-adding agent for leather.
Embodiment 5:
100.0g soybean oil and the adding of 10.0g Monoethanolamine MEA BASF are equipped with in the dry four-hole glass flask of agitator, prolong, are warming up to 140 ℃ and carry out amidate action, reaction is carried out obtaining the amidation soybean oil that hydroxyl value is 158.34mgKOH/g behind the 3.0h.In the amidation soybean oil, add 5.50g (amidation soybean oil heavy 5%) Span80, the amount of the total hydroxylated material of system this moment is 0.3319mol, slowly add then with the 36.70g composite dispersing agent (the chlorination rape oil fatty acid methyl esters of m[chlorinity 20%]: the m[15 white oil]=2.5: 1) dissolved 21.59g P 2O 5(OH: P 2O 5[mol]=1: 0.46) phosphorylation, keeping temperature of reaction is 80 ℃, carries out 2.0h.Add 4.95g water (H then 2O: P 2O 5[mol]=1.5: 1) hydrolysis, promptly obtain phosphorylation amidation soybean oil.System is cooled to 55 ℃ then, to wherein adding the special-purpose alkyl sulfonamide of 99.3g leather, the synthetic stuffing material of 99.3g Syn both sexes and 19.86g soybean lecithin, stir the back to the sodium hydroxide solution neutralization that wherein drips 30%, the pH value of system is adjusted to about 7.0, be adjusted to working substance content 〉=70% to wherein adding 9g water then, after water injection, insulation continues to stir 1.0h, promptly obtains composite phosphate grease-adding agent for leather.
Embodiment 6:
50.0g rapeseed oil, 50.0g plam oil and the adding of 9.0g Monoethanolamine MEA BASF are equipped with in the dry four-hole glass flask of agitator, prolong, be warming up to 140 ℃ and carry out amidate action, reaction is carried out obtaining the amidation vegetables oil that hydroxyl value is 143.81mgKOH/g behind the 2.5h.In the amidation vegetables oil, add 5.45g (amidation vegetables oil heavy 5%) Span80, the amount of the total hydroxylated material of system this moment is 0.3006mol, slowly add then with the 33.23g composite dispersing agent (the chlorination rape oil fatty acid methyl esters of m[chlorinity 20%]: the m[10 white oil]=4.0: 1) dissolved 19.55g P 2O 5(OH: P 2O 5[mol]=1: 0.46) phosphorylation, keeping temperature of reaction is 80 ℃, carries out 2.0h.Add 4.23g water (H then 2O: P 2O 5[mol]=1.6: 1) hydrolysis, promptly obtain phosphorylation amidation vegetables oil.System is cooled to 60 ℃ then, to wherein adding the special-purpose alkyl sulfonamide of 76.20g leather, the synthetic stuffing material of 95.26g Syn both sexes and 38.10g soybean lecithin, stir the back to the sodium hydroxide solution neutralization that wherein drips 30%, the pH value of system is adjusted to about 7.0, be adjusted to working substance content 〉=70% to wherein adding 14g water then, after water injection, insulation continues to stir 1.0h, promptly obtains composite phosphate grease-adding agent for leather.
Embodiment 7:
100.0g plam oil and the adding of 7.0g Monoethanolamine MEA BASF are equipped with in the dry four-hole glass flask of agitator, prolong, are warming up to 135 ℃ and carry out amidate action, reaction is carried out obtaining the amidation plam oil that hydroxyl value is 113.94mgKOH/g behind the 2.5h.In the amidation plam oil, add 3.21g (amidation plam oil heavy 3%) Span80, the amount of the total hydroxylated material of system this moment is 0.2292mol, slowly add then with the 19.44g composite dispersing agent (the chlorination rape oil fatty acid methyl esters of m[chlorinity 20%]: the m[15 white oil]=2.0: 1) P of dissolved 12.96g 2O 5(OH: P 2O 5[mol]=1: 0.4) phosphorylation, keeping temperature of reaction is 75 ℃, carries out 2.0h.Add 2.47g water (H then 2O: P 2O 5[mol]=1.5: 1) hydrolysis, promptly obtain phosphorylation amidation plam oil.System is cooled to 55 ℃ then, to wherein adding the special-purpose alkyl sulfonamide of 108.8g leather, the synthetic stuffing material of 72.54g Syn both sexes and 36.27g soybean lecithin, stir the back to the sodium hydroxide solution neutralization that wherein drips 30%, the pH value of system is adjusted to about 7.0, be adjusted to working substance content 〉=70% to wherein adding 12g water then, after water injection, insulation continues to stir 1.0h, promptly obtains composite phosphate grease-adding agent for leather.
Embodiment 8:
100.0g rapeseed oil and the adding of 11.0g Monoethanolamine MEA BASF are equipped with in the dry four-hole glass flask of agitator, prolong, are warming up to 140 ℃ and carry out amidate action, reaction is carried out obtaining the amidation rapeseed oil that hydroxyl value is 172.6mgKOH/g behind the 2.5h.In the amidation rapeseed oil, add 4.44g (amidation rapeseed oil heavy 4%) Span80, the amount of the total hydroxylated material of system this moment is 0.3582mol, slowly add then with the 36.464g composite dispersing agent (the chlorination rape oil fatty acid methyl esters of m[chlorinity 20%]: the m[5 white oil]=3.5: 1) P of dissolved 22.79g 2O 5(OH: P 2O 5[mol]=1: 0.45) phosphorylation, keeping temperature of reaction is 75 ℃, carries out 2.0h.Add 4.64g water (H then 2O: P 2O 5[mol]=1.6: 1) hydrolysis, promptly obtain phosphorylation amidation rapeseed oil.System is cooled to 55 ℃ then, to wherein adding the special-purpose alkyl sulfonamide of 71.73g leather, the synthetic stuffing material of 71.73g Syn both sexes and 35.87g soybean lecithin, stir the back to the sodium hydroxide solution neutralization that wherein drips 30%, the pH value of system is adjusted to about 7.0, be adjusted to working substance content 〉=70% to wherein adding 16g water then, after water injection, insulation continues to stir 1.0h, promptly obtains composite phosphate grease-adding agent for leather.
Embodiment 9:
100.0g soybean oil and the adding of 6.0g Monoethanolamine MEA BASF are equipped with in the dry four-hole glass flask of agitator, prolong, are warming up to 135 ℃ and carry out amidate action, reaction is carried out obtaining the amidation soybean oil that hydroxyl value is 98.59mgKOH/g behind the 2.5h.In the amidation soybean oil, add 2.12g (amidation soybean oil heavy 2%) Span80, the amount of the total hydroxylated material of system this moment is 0.1942mol, slowly add then with the 10.98g composite dispersing agent (the chlorination rape oil fatty acid methyl esters of m[chlorinity 20%]: the m[5 white oil]=2.5: 1) dissolved 10.98g P 2O 5(OH: P 2O 5[mol]=1: 0.4) phosphorylation, keeping temperature of reaction is 80 ℃, carries out 2.0h.Add 2.24g water (H then 2O: P 2O 5[mol]=1.6: 1) hydrolysis, promptly obtain phosphorylation amidation soybean oil.System is cooled to 60 ℃ then, to wherein adding the special-purpose alkyl sulfonamide of 52.93g leather, the synthetic stuffing material of 52.93g Syn both sexes and 26.5g soybean lecithin, stir the back to the sodium hydroxide solution neutralization that wherein drips 30%, the pH value of system is adjusted to about 7.0, be adjusted to working substance content 〉=70% to wherein adding 11g water then, after water injection, insulation continues to stir 1.0h, promptly obtains composite phosphate grease-adding agent for leather.
Embodiment 10:
100.0g rapeseed oil and the adding of 7.0g Monoethanolamine MEA BASF are equipped with in the dry four-hole glass flask of agitator, prolong, are warming up to 135 ℃ and carry out amidate action, reaction is carried out obtaining the amidation rapeseed oil that hydroxyl value is 113.94mgKOH/g behind the 2.5h.In the amidation rapeseed oil, add 10.7g (amidation rapeseed oil heavy 10%) Span80, the amount of the total hydroxylated material of system this moment is 0.2575mol, slowly add then with the 25.49g composite dispersing agent (the chlorination rape oil fatty acid methyl esters of m[chlorinity 20%]: the m[15 white oil]=3.0: 1) dissolved 12.74g P 2O 5(OH: P 2O 5[mol]=1: 0.35) phosphorylation, keeping temperature of reaction is 80 ℃, carries out 2.0h.Add 3.24g water (H then 2O: P 2O 5[mol]=2.0: 1) hydrolysis, promptly obtain phosphorylation amidation rapeseed oil.System is cooled to 60 ℃ then, to wherein adding the special-purpose alkyl sulfonamide of 79.58g leather, the synthetic stuffing material of 119.37g Syn both sexes and 39.75g soybean lecithin, stir the back to the sodium hydroxide solution neutralization that wherein drips 30%, the pH value of system is adjusted to about 7.0, be adjusted to working substance content 〉=70% to wherein adding 15g water then, after water injection, insulation continues to stir 1.0h, promptly obtains composite phosphate grease-adding agent for leather.
Embodiment 11:
100.0g plam oil and the adding of 7.0g Monoethanolamine MEA BASF are equipped with in the dry four-hole glass flask of agitator, prolong, are warming up to 135 ℃ and carry out amidate action, reaction is carried out obtaining the amidation plam oil that hydroxyl value is 113.94mgKOH/g behind the 2.5h.In the amidation plam oil, add 1.07g (amidation plam oil heavy 1%) Span80, the amount of the total hydroxylated material of system this moment is 0.2210mol, slowly add then with the 23.43g composite dispersing agent (the chlorination rape oil fatty acid methyl esters of m[chlorinity 20%]: the m[10 white oil]=2.5: 1) dissolved 15.62g P 2O 5(OH: P 2O 5[mol]=1: 0.5) phosphorylation, keeping temperature of reaction is 80 ℃, carries out 2.0h.Add 2.98g water (H then 2O: P 2O 5[mol]=1.5: 1) hydrolysis, promptly obtain phosphorylation amidation plam oil.System is cooled to 60 ℃ then, to wherein adding the special-purpose alkyl sulfonamide of 83.37g leather, the synthetic stuffing material of 83.37g Syn both sexes and 16.67g soybean lecithin, stir the back to the sodium hydroxide solution neutralization that wherein drips 30%, the pH value of system is adjusted to about 7.0, be adjusted to working substance content 〉=70% to wherein adding 13g water then, after water injection, insulation continues to stir 1.0h, promptly obtains composite phosphate grease-adding agent for leather.
Embodiment 12:
20.0g plam oil, 40.0g soybean oil, 40.0g rapeseed oil and the adding of 7.0g Monoethanolamine MEA BASF are equipped with in the dry four-hole glass flask of agitator, prolong, be warming up to 135 ℃ and carry out amidate action, reaction is carried out obtaining the amidation plam oil that hydroxyl value is 113.94mgKOH/g behind the 2.5h.In the amidation plam oil, add 1.07g (amidation plam oil heavy 1%) Span80, the amount of the total hydroxylated material of system this moment is 0.2210mol, slowly add then with the 23.43g composite dispersing agent (the chlorination rape oil fatty acid methyl esters of m[chlorinity 20%]: the m[10 white oil]=2.5: 1) dissolved 15.62g P 2O 5(OH: P 2O 5[mol]=1: 0.5) phosphorylation, keeping temperature of reaction is 80 ℃, carries out 2.0h.Add 2.98g water (H then 2O: P 2O 5[mol]=1.5: 1) hydrolysis, promptly obtain phosphorylation amidation plam oil.System is cooled to 60 ℃ then, to wherein adding the special-purpose alkyl sulfonamide of 83.37g leather, the synthetic stuffing material of 83.37g Syn both sexes and 16.67g soybean lecithin, stir the back to the sodium hydroxide solution neutralization that wherein drips 30%, the pH value of system is adjusted to about 7.0, be adjusted to working substance content 〉=70% to wherein adding 13g water then, after water injection, insulation continues to stir 1.0h, promptly obtains composite phosphate grease-adding agent for leather.

Claims (29)

1. a composite phosphate leather greasing profit contains phosphorylation amidation vegetables oil, the special-purpose alkyl sulfonamide of leather and soybean lecithin, it is characterized in that, also contains the synthetic stuffing material of Syn both sexes; Described phosphorylation amidation vegetables oil, is used in the presence of oil-soluble emulsifier and is adopted composite dispersing agent dispersive P after the Monoethanolamine MEA BASF amidation by vegetables oil 2O 5Phosphorylation obtains through hydrolysis again; The ratio of each component is: phosphorylation amidation vegetables oil 40%~50%, stuffing material 20%~30% is synthesized in the Syn both sexes, the special-purpose alkyl sulfonamide 20%~25% of leather, soybean lecithin 5%~10%.
2. the preparation method of a kind of composite phosphate grease-adding agent for leather as claimed in claim 1 comprises amidation, phosphorylation, hydrolysis and composite step; Described amidation is with Monoethanolamine MEA BASF vegetables oil to be carried out the amidation modification, and the amidation modification is 120 ℃~150 ℃ in temperature of reaction, reacts 2.0h~3.0h under the catalyst-free condition; It is characterized in that,
(1) amidation: described vegetables oil is rapeseed oil, plam oil or soybean oil, or the mixture of rapeseed oil, plam oil and soybean oil three arbitrary proportion; The mass ratio of vegetables oil and Monoethanolamine MEA BASF is 100: 6~11 during amidation; React the amidation vegetables oil, reaction finishes the hydroxyl value that the amidation vegetables oil is measured in the back;
(2) phosphorylation: after the amidation vegetables oil that described step (1) is obtained is cooled to about 70 ℃, add oil-soluble emulsifier; Described oil-soluble emulsifier is selected tensio-active agent Span80 for use, and the consumption of Span80 is 1%~10% of an amidation vegetables oil;
Selecting the composite inert oil plant then for use is composite dispersing agent, and described composite inert oil plant is made up of the chlorination rape oil fatty acid methyl esters and the white oil of chlorinity 20%, and its mass ratio is: the chlorination rape oil fatty acid methyl esters of chlorinity 20%: white oil=2.0~4.0: 1.0; With adopting described composite inert oil plant dispersive P 2O 5Phosphorylation, P 2O 5With the mass ratio of composite inert oil plant be 1.0: 1.0~2.0; Described employing composite inert oil plant dispersive P 2O 5Add-on be: amidation vegetables oil hydroxyl and Span80 hydroxyl sum and P 2O 5Mol ratio be 1.0: 0.35~0.5;
Temperature of reaction is 60 ℃~90 ℃, and the reaction times is 2.0h~3.0h;
(3) hydrolysis: add a spot of water in described step (2) products therefrom, adding the amount of entry and the mol ratio of P2O5 is 1.5~2.0: 1.0, promptly obtains phosphorylation amidation vegetables oil;
(4) composite: the phosphorylation amidation vegetables oil that described step (3) is obtained is cooled to 50 ℃~60 ℃, adds the synthetic stuffing material of Syn both sexes, the special-purpose alkyl sulfonamide of leather and soybean lecithin; The ratio of each component according to claim 1; Composite temperature is 40 ℃~70 ℃; Mix the aqueous sodium hydroxide solution neutralization of back adding 30%, the pH value of regulation system is 6.0~8.0 simultaneously; Then in system, add a certain amount of water again, regulate working substance content 〉=70% of product; Continue to stir 0.5h~2.0h, promptly obtain the final product composite phosphate grease-adding agent for leather.
3. the preparation method of a kind of composite phosphate grease-adding agent for leather as claimed in claim 2 is characterized in that, the mass ratio of vegetables oil and Monoethanolamine MEA BASF is 100: 7~10 during amidation.
4. as the preparation method of claim 2 or 3 described a kind of composite phosphate grease-adding agent for leather, it is characterized in that the consumption of Span80 is 2%~7% of an amidation vegetables oil.
5. as the preparation method of claim 2 or 3 described a kind of composite phosphate grease-adding agent for leather, it is characterized in that the consumption of Span80 is 3%~5% of an amidation vegetables oil.
6. as the preparation method of claim 2 or 3 described a kind of composite phosphate grease-adding agent for leather, it is characterized in that the chlorination rape oil fatty acid methyl esters of chlorinity 20%: the mass ratio of white oil is 2.5~3.5: 1.0; P 2O 5With the mass ratio of composite inert oil plant be 1.0: 1.4~1.8; Amidation vegetables oil hydroxyl and Span80 hydroxyl sum and P 2O 5Mol ratio be 1.0: 0.4~0.48.
7. the preparation method of a kind of composite phosphate grease-adding agent for leather as claimed in claim 4 is characterized in that, the chlorination rape oil fatty acid methyl esters of chlorinity 20%: the mass ratio of white oil is 2.5~3.5: 1.0; P 2O 5With the mass ratio of composite inert oil plant be 1.0: 1.4~1.8; Amidation vegetables oil hydroxyl and Span80 hydroxyl sum and P 2O 5Mol ratio be 1.0: 0.4~0.48.
8. the preparation method of a kind of composite phosphate grease-adding agent for leather as claimed in claim 5 is characterized in that, the chlorination rape oil fatty acid methyl esters of chlorinity 20%: the mass ratio of white oil is 2.5~3.5: 1.0; P 2O 5With the mass ratio of composite inert oil plant be 1.0: 1.4~1.8; Amidation vegetables oil hydroxyl and Span80 hydroxyl sum and P 2O 5Mol ratio be 1.0: 0.4~0.48.
9. as the preparation method of claim 2,3,7 or 8 described a kind of composite phosphate grease-adding agent for leather, it is characterized in that the temperature of reaction of phosphorylation is 65 ℃~85 ℃.
10. the preparation method of a kind of composite phosphate grease-adding agent for leather as claimed in claim 4 is characterized in that, the temperature of reaction of phosphorylation is 65 ℃~85 ℃.
11. the preparation method of a kind of composite phosphate grease-adding agent for leather as claimed in claim 5 is characterized in that, the temperature of reaction of phosphorylation is 65 ℃~85 ℃.
12. the preparation method of a kind of composite phosphate grease-adding agent for leather as claimed in claim 6 is characterized in that, the temperature of reaction of phosphorylation is 65 ℃~85 ℃.
13. the preparation method as claim 2,3,7 or 8 described a kind of composite phosphate grease-adding agent for leather is characterized in that, the temperature of reaction of phosphorylation is 70 ℃~85 ℃.
14. the preparation method of a kind of composite phosphate grease-adding agent for leather as claimed in claim 4 is characterized in that, the temperature of reaction of phosphorylation is 70 ℃~85 ℃.
15. the preparation method of a kind of composite phosphate grease-adding agent for leather as claimed in claim 5 is characterized in that, the temperature of reaction of phosphorylation is 70 ℃~85 ℃.
16. the preparation method of a kind of composite phosphate grease-adding agent for leather as claimed in claim 6 is characterized in that, the temperature of reaction of phosphorylation is 70 ℃~85 ℃.
17. the preparation method as claim 2,3,7 or 8 described a kind of composite phosphate grease-adding agent for leather is characterized in that, composite temperature is 50 ℃~65 ℃; The time of continuing to stir is 1.0h~1.5h.
18. a kind of preparation method who makes the type phosphate aster leather currying agent again as claimed in claim 4 is characterized in that, composite temperature is 50 ℃~65 ℃; The time of continuing to stir is 1.0h~1.5h.
19. the preparation method of a kind of composite phosphate grease-adding agent for leather as claimed in claim 5 is characterized in that, composite temperature is 50 ℃~65 ℃; The time of continuing to stir is 1.0h~1.5h.
20. the preparation method of a kind of composite phosphate grease-adding agent for leather as claimed in claim 6 is characterized in that, composite temperature is 50 ℃~65 ℃; The time of continuing to stir is 1.0h~1.5h.
21. the preparation method of a kind of composite phosphate grease-adding agent for leather as claimed in claim 9 is characterized in that, composite temperature is 50 ℃~65 ℃; The time of continuing to stir is 1.0h~1.5h.
22. the preparation method as arbitrary described a kind of composite phosphate grease-adding agent for leather of claim 10~12 is characterized in that composite temperature is 50 ℃~65 ℃; The time of continuing to stir is 1.0h~1.5h.
23. the preparation method as claim 2,3,7,8,10~12,14~16, arbitrary described a kind of composite phosphate grease-adding agent for leather of 18~22 is characterized in that described white oil is No. 5 white oils, No. 10 white oils or No. 15 white oils.
24. the preparation method of a kind of composite phosphate grease-adding agent for leather as claimed in claim 4 is characterized in that, described white oil is No. 5 white oils, No. 10 white oils or No. 15 white oils.
25. the preparation method of a kind of composite phosphate grease-adding agent for leather as claimed in claim 5 is characterized in that, described white oil is No. 5 white oils, No. 10 white oils or No. 15 white oils.
26. the preparation method of a kind of composite phosphate grease-adding agent for leather as claimed in claim 6 is characterized in that, described white oil is No. 5 white oils, No. 10 white oils or No. 15 white oils.
27. the preparation method of a kind of composite phosphate grease-adding agent for leather as claimed in claim 9 is characterized in that, described white oil is No. 5 white oils, No. 10 white oils or No. 15 white oils.
28. the preparation method of a kind of composite phosphate grease-adding agent for leather as claimed in claim 13 is characterized in that, described white oil is No. 5 white oils, No. 10 white oils or No. 15 white oils.
29. the preparation method of a kind of composite phosphate grease-adding agent for leather as claimed in claim 17 is characterized in that, described white oil is No. 5 white oils, No. 10 white oils or No. 15 white oils.
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Publication number Priority date Publication date Assignee Title
CN101643802B (en) * 2008-08-28 2012-09-05 齐河力厚化工有限公司 Modified phospholipid composite fat liquor and preparation thereof
CN101691619B (en) * 2009-10-19 2012-12-19 浙江赞宇科技股份有限公司 Method for preparing leather fatliquoring agent
CN101760570B (en) * 2009-12-29 2013-05-01 温州大学 Composite leather greasing agent and preparation method thereof
CN102703623A (en) * 2012-06-11 2012-10-03 科凯精细化工(上海)有限公司 Novel greasing agent for synthetic leather and preparation method for novel greasing agent
CN104651546A (en) * 2013-11-21 2015-05-27 谈丽娜 Composite-type phosphate leather fatliquor and preparation method thereof
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CN106282443B (en) * 2016-08-18 2018-07-13 中国皮革和制鞋工业研究院(晋江)有限公司 A kind of preparation method of phosphate fat-liquoring agent
CN108774652A (en) * 2018-07-06 2018-11-09 张玲 A kind of preparation method of biodegradation fatting agent

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU1751220A1 (en) * 1990-06-19 1992-07-30 Курское научно-производственное кожевенно-обувное объединение Composition for leather stuffing
CN1098141A (en) * 1993-07-24 1995-02-01 吴强 Phosphate type leather currying agent and synthetic method thereof
RU2043422C1 (en) * 1993-07-30 1995-09-10 Научно-производственное объединение "Центральный научно-исследовательский институт кожевенно-обувной промышленности" Fat-liquoring composition
CN1580288A (en) * 2003-08-11 2005-02-16 阮文娟 Method for manufacturing leather fattening agent
EP1621640A1 (en) * 2004-07-13 2006-02-01 Zschimmer & Schwarz GmbH & Co KG Chemische Fabriken Agent for the hydrophobic treatment of leather

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU1751220A1 (en) * 1990-06-19 1992-07-30 Курское научно-производственное кожевенно-обувное объединение Composition for leather stuffing
CN1098141A (en) * 1993-07-24 1995-02-01 吴强 Phosphate type leather currying agent and synthetic method thereof
RU2043422C1 (en) * 1993-07-30 1995-09-10 Научно-производственное объединение "Центральный научно-исследовательский институт кожевенно-обувной промышленности" Fat-liquoring composition
CN1580288A (en) * 2003-08-11 2005-02-16 阮文娟 Method for manufacturing leather fattening agent
EP1621640A1 (en) * 2004-07-13 2006-02-01 Zschimmer & Schwarz GmbH & Co KG Chemische Fabriken Agent for the hydrophobic treatment of leather

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