CN106435054B - Greasing-retanning agnt of leather and preparation method - Google Patents

Greasing-retanning agnt of leather and preparation method Download PDF

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Publication number
CN106435054B
CN106435054B CN201610791912.4A CN201610791912A CN106435054B CN 106435054 B CN106435054 B CN 106435054B CN 201610791912 A CN201610791912 A CN 201610791912A CN 106435054 B CN106435054 B CN 106435054B
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leather
retanning
greasing
hydroxyl
agnt
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CN106435054A (en
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陈华
严建林
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SICHUAN DOWELL TECHNOLOGY CO LTD
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SICHUAN DOWELL TECHNOLOGY CO LTD
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    • CCHEMISTRY; METALLURGY
    • C14SKINS; HIDES; PELTS; LEATHER
    • C14CCHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C3/00Tanning; Compositions for tanning
    • C14C3/02Chemical tanning
    • C14C3/08Chemical tanning by organic agents
    • C14C3/22Chemical tanning by organic agents using polymerisation products
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04Acids; Metal salts or ammonium salts thereof
    • C08F220/06Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10Esters
    • C08F222/12Esters of phenols or saturated alcohols
    • C08F222/16Esters having free carboxylic acid groups, e.g. monoalkyl maleates or fumarates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10Esters
    • C08F222/12Esters of phenols or saturated alcohols
    • C08F222/20Esters containing oxygen in addition to the carboxy oxygen
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10Esters
    • C08F222/12Esters of phenols or saturated alcohols
    • C08F222/22Esters containing nitrogen

Abstract

The present invention provides a kind of preparation methods of greasing-retanning agnt of leather, include the following steps:A) alcohols reacts to obtain the first intermediate with maleic anhydride;Aminated compounds of the natural oil through hydroxyl is modified, obtains the compound of hydroxyl;The compound of the hydroxyl is reacted with maleic anhydride, obtains the second intermediate;B) under the action of reaction medium, emulsifier and initiator polymerization reaction occurs for first intermediate, the second intermediate and vinyl monomer, obtains greasing-retanning agnt of leather;The polymeric reaction temperature is 120~160 DEG C, and the polymerization reaction time is 3~9h.Under specified conditions of the invention, vinyl monomer can mutually polymerize, and assign leather excellent filling effect, increase leather is plentiful, grain compactibility etc.;Meanwhile first intermediate, the second intermediate and vinyl monomer mutually polymerize, and obtain greasing-retanning agnt of leather, retanning are carried out to leather using it, so that the flexibility of leather, richness and uniformity are preferable.

Description

Greasing-retanning agnt of leather and preparation method
Technical field
The present invention relates to leather technology fields, more particularly, to a kind of greasing-retanning agnt of leather and preparation method.
Background technique
Retanning is the committed step in process hides, by retanning can improve the pliability of leather, the smooth careful property of grain, Wearability, the qualitative and richness of embossing etc.;And by carrying out leather retanning, the leather of different-style can be formed, preferably Meet the needs of market is to leather goods.
Greasing-retanning agnt of leather had both maintained the excellent performance of fatting agent, kept leather hand feeling softness fine and glossy, and had retanning It is plentiful and elastic to assign leather goods for the characteristic of agent.In the prior art, there are mainly two types of lubricating retanning agent preparation methods:1, fat Alcohol and alcohol ether are esterified with cis-butenedioic anhydride, then are graft-polymerized with vinyl monomer;2, natural oil carries out amidation, with cis-butenedioic anhydride ester Change, then is graft-polymerized with vinyl monomer.And the former stuffing effect is poor.Latter reaction leads low, and monomer residue is more, polymer composition And distributional difference is very big, leads to that retanning agent product is easily layered and stability is poor between batch, makes applied to leather retanning Pliability, richness and the uniformity for obtaining leather are poor.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that, a kind of preparation method of greasing-retanning agnt of leather is provided, The lubricating retanning agent that the preparation method of greasing-retanning agnt of leather provided by the invention is prepared carries out retanning to leather, so that skin The flexibility of leather, richness and uniformity are preferable
The present invention provides a kind of preparation methods of greasing-retanning agnt of leather, include the following steps:
A) alcohols reacts to obtain the first intermediate with maleic anhydride;
Aminated compounds of the natural oil through hydroxyl is modified, obtains the compound of hydroxyl;The compound of the hydroxyl It is reacted with maleic anhydride, obtains the second intermediate;
B) the work of first intermediate, the second intermediate and vinyl monomer in reaction medium, emulsifier and initiator With lower generation polymerization reaction, greasing-retanning agnt of leather is obtained;The polymeric reaction temperature is 120~160 DEG C, the polymerization reaction Time is 3~9h.
Preferably, the step B) reaction medium be water.
Preferably, the vinyl monomer is that the mode being added dropwise is added, and time for adding is 2~6h.
Preferably, the vinyl monomer be selected from acrylicacidandesters class, oleic acid vinyl acetate, vinylacetate, styrene, One of acrylonitrile and acrylamide are a variety of.
Preferably, the initiator is selected from ammonium persulfate, one or more of sodium peroxydisulfate and potassium peroxydisulfate.
Preferably, the alcohols can be cell alcohol or polyalcohol;The cell alcohol be selected from ethyl alcohol, butanol, isooctanol, The fatty alcohol of C12~14, the fatty alcohol of C16~18 and C20 fatty alcohol it is one or more;The polyalcohol is selected from dihydric alcohol or ternary One of alcohol is a variety of.Preferably, the molar ratio of the alcohols and maleic anhydride is (1~2):1.
Preferably, the natural oil is selected from vegetable oil and animal oil.
Preferably, the aminated compounds of the hydroxyl is selected from one kind or more of ethanol amine, diethanol amine and triethanolamine Kind.
The present invention provides a kind of greasing-retanning agnt of leather, the preparation method as described in above-mentioned technical proposal is prepared.
Compared with prior art, the present invention provides a kind of preparation method of greasing-retanning agnt of leather, include the following steps: A) alcohols reacts to obtain the first intermediate with maleic anhydride;Aminated compounds of the natural oil through hydroxyl is modified, obtains hydroxyl Compound;The compound of the hydroxyl is reacted with maleic anhydride, obtains the second intermediate;B) first intermediate, Under the action of reaction medium, emulsifier and initiator polymerization reaction occurs for two intermediates and vinyl monomer, obtains leather and adds Rouge retanning agent;The polymeric reaction temperature is 120~160 DEG C, and the polymerization reaction time is 3~9h.Of the invention above-mentioned Under specified conditions, vinyl monomer can mutually polymerize, and assign leather excellent filling effect, increase leather is plentiful, grain consolidation Property and water-fastness and waterproofness etc.;Meanwhile first intermediate, the second intermediate and vinyl monomer mutually polymerize, and finally obtain Greasing-retanning agnt of leather, using its to leather carry out retanning so that the flexibility of leather, richness and uniformity are preferable.
Specific embodiment
The present invention provides a kind of preparation methods of greasing-retanning agnt of leather, include the following steps:
A) alcohols reacts to obtain the first intermediate with maleic anhydride;
Aminated compounds of the natural oil through hydroxyl is modified, obtains the compound of hydroxyl;The compound of the hydroxyl It is reacted with maleic anhydride, obtains the second intermediate;
B) the work of first intermediate, the second intermediate and vinyl monomer in reaction medium, emulsifier and initiator With lower generation polymerization reaction, greasing-retanning agnt of leather is obtained;The polymeric reaction temperature is 120~160 DEG C, the polymerization reaction Time is 3~9h.
In the present invention, alcohols is reacted first to obtain the first intermediate with maleic anhydride.
In the present invention, the alcohols preferably can be cell alcohol or polyalcohol;The cell alcohol is preferably selected from ethyl alcohol, fourth The fatty alcohol of alcohol, isooctanol, C12~14, the fatty alcohol of C16~18 and C20 fatty alcohol it is one or more;More preferably it is selected from C12 The fatty alcohol of~14 fatty alcohols, C16~18 and C20 fatty alcohol it is one or more;
The polyalcohol is preferably selected from one of dihydric alcohol and trihydroxylic alcohol or a variety of;It is more preferably selected from ethylene glycol, fourth two One of alcohol, pentanediol, hexylene glycol, glycerine, PEG and PPG or a variety of;It is most preferably selected from ethylene glycol, butanediol, the third three One of alcohol, PEG and PPG or a variety of.Wherein, PEG includes but is not limited to PEG200, PEG400, PEG600, the PPG packet It includes but is not limited to PPG200, PPG400, PPG800.
In the present invention, the molar ratio of the alcohols and maleic anhydride is preferably (1~2):1, the reaction temperature is preferred It is 80~110 DEG C;More preferably 85~95 DEG C;The reaction time is preferably 2~5h;More preferably 4~5h.
In the present invention, above-mentioned alcohols is reacted with maleic anhydride, obtains maleic anhydride monoesters or dibasic acid esters, and single dibasic acid esters is mixed Close object;It is the important component for synthesizing lubricating retanning agent, gives leather excellent light resistance, water-wash resistance, good waterproof effect And light effect.
Aminated compounds of the natural oil through hydroxyl is modified, obtains the compound of hydroxyl;The compound of the hydroxyl It is reacted with maleic anhydride, obtains the second intermediate.
Aminated compounds of the natural oil through hydroxyl is modified, obtains the compound of hydroxyl;Wherein, natural oil is preferably selected from One of vegetable oil and animal oil are a variety of;The vegetable oil is preferably selected from palm oil, rice bran oil, rapeseed oil, peanut oil, beans One of oil and cottonseed oil are a variety of;The animal oil is preferably selected from one in neat's foot oil, lard, butter, sheep oil and fish oil Kind is a variety of.
Natural oil of the present invention can be above-mentioned natural oil, while may be natural oil adjunct, such as fatty acid methyl Ester, rape oil acid, oil extracted from rice husks acid.
The aminated compounds of the hydroxyl is preferably selected from polyhydric alcohol amine;It is more preferably selected from ethanol amine, diethanol amine and three Ethanol amine it is one or more.
The molar ratio of the aminated compounds of the natural oil and hydroxyl is preferably 1:(1~3);The modification temperature is preferred It is 110~140 DEG C;The modification time is preferably 2~5h;The modification temperature is more preferably 115~125 DEG C, the modification Time is more preferably 3.5~4.5h.
After obtaining the compound of hydroxyl, the compound of the hydroxyl is reacted with maleic anhydride, obtains the second intermediate.
The compound of hydroxyl of the present invention and the molar ratio of maleic anhydride are preferably (1~2):(1~3);It is described anti- Answering temperature is preferably 80~110 DEG C, and the reaction time is preferably 2~3h.
Natural oil of the present invention is reacted with maleic anhydride again through the aminated compounds modification of hydroxyl, is obtained among second Body gives leather excellent soft effect, splendid moist feel, is that the important component of synthesis lubricating retanning agent is another important Component.
After obtaining the first intermediate and the second intermediate, by first intermediate, the second intermediate and vinyl monomer Polymerization reaction occurs under the action of reaction medium, emulsifier and initiator, obtains greasing-retanning agnt of leather;The polymerization reaction Temperature is 120~160 DEG C, and the polymerization reaction time is 3~9h.
In the present invention, the vinyl monomer is preferably selected from acrylicacidandesters class, oleic acid vinyl acetate, vinyl acetate Ester, styrene, acrylonitrile and acrylamide;The acrylicacidandesters class is preferably selected from acrylic acid, methacrylic acid, acrylic acid Different monooctyl ester, acrylic acid C1~C18 ester and methacrylate it is one or more;In the present invention, the reaction medium is preferred For water;More preferably deionized water.The mass percent that the additive amount of the water accounts for polymer total amount is preferably 60~70%.
The present invention adopts water as reaction medium, more environment-friendly and safer without using reacting under conditions of organic solvent.
In the present invention, the emulsifier is anion emulsifier, including but not limited to lauryl sodium sulfate and alkyl Sodium sulfonate.The initiator is preferably selected from ammonium persulfate, one or more of sodium peroxydisulfate and potassium peroxydisulfate.The emulsifier Additive amount to account for the first intermediate, the second intermediate and vinyl monomer gross mass percentage be preferably 0.5~5.0%.It is described It is preferably 1.0~10% that the additive amount of initiator, which accounts for the first intermediate, the second intermediate and vinyl monomer gross mass percentage,.
The present invention is for the reaction vessel without limiting, it is preferred to use autoclave carries out.
The reaction is preferably specially to mix the first intermediate and the second intermediate, and vinyl monomer is added, and heat preservation is anti- It answers.
The vinyl monomer is preferably that the mode being added dropwise is added, and the time for adding is preferably 2~6h;More preferably 3 ~5h;Most preferably 3~4h.
The insulation reaction temperature is 120~160 DEG C;Preferably 125~155 DEG C;More preferably 125~155 DEG C;It is described The insulation reaction time is preferably 1~3h;More preferably 1~1.5h.
The molar ratio of first intermediate of the present invention, the second intermediate and vinyl monomer is preferably (1~2):(1~ 2):(1~6).In the present invention, after the completion of above-mentioned polymerization reaction, it is also preferable to include:It neutralizes, i.e., adjusts pH value with liquid alkaline.
The liquid alkaline is preferably selected from one or more of sodium hydroxide, ammonium hydroxide, ethanol amine, diethanol amine, triethanolamine. In the present invention, the mass concentration of the sodium hydroxide is preferably 28~32%;More preferably 30%~32%;The ammonium hydroxide Mass concentration is preferably 18%~22%;More preferably 20%~22%.
The neutralization temperature is preferably 30~45 DEG C;More preferably 35~40 DEG C;The adjusting pH value is preferably to 4~7;More It is preferred that 6.0~6.5.
Under the conditions of above-mentioned specific temperature of the invention, time, dropwise addition, the first intermediate, the second intermediate and vinyl Monomer mutually polymerize, and reactivity is big, and reaction probabilities are high, and seldom, finally obtained leather greasing is multiple for maleic anhydride esters residual Tanning agent flexibility, richness and uniformity are preferable.
In addition, under the above specified conditions further including the autohemagglutination and ethylene of the autohemagglutination of the first intermediate, the second intermediate The autohemagglutination of class monomer, wherein the autohemagglutination of the first intermediate, gives leather excellent light resistance, water-wash resistance, good waterproof effect Fruit and light effect;The autohemagglutination of second intermediate gives leather excellent soft effect, splendid moist feel;Vinyl The autohemagglutination of monomer assigns leather excellent filling effect, and it is plentiful to further increase leather, grain compactibility and water-fastness and waterproof Property etc..
The present invention provides a kind of greasing-retanning agnt of leather, the preparation method as described in above-mentioned technical proposal is prepared.
The present invention is by changing maleic anhydride synthesizing ester monomer, the modified esters monomer of maleic anhydride natural oil, propylene Acid and vinyl monomer type;The mass fraction of molar ratio;Or maleic anhydride synthesizing ester monomer and acrylicacidandesters are used, It is splendid and to leather greasing to obtain stability for the modified esters monomer of maleic anhydride natural oil, and this technique is used to synthesize The good polymer of retanning comprehensive performance;This synthesis technology is equally used, by adjusting different dosage and proportion, can be synthesized The fatting agent of retanning is biased toward out, can also synthesize the retanning agent for biasing toward stuffing;In conclusion its synthetic route belongs to The protection scope of this patent.
The present invention provides a kind of preparation methods of greasing-retanning agnt of leather, include the following steps:A) alcohols and maleic acid Anhydride reactant obtains the first intermediate;Aminated compounds of the natural oil through hydroxyl is modified, obtains the compound of hydroxyl;It is described to contain The compound of hydroxyl is reacted with maleic anhydride, obtains the second intermediate;B) first intermediate, the second intermediate and vinyl Under the action of reaction medium, emulsifier and initiator polymerization reaction occurs for monomer, obtains greasing-retanning agnt of leather;The polymerization Reaction temperature is 120~160 DEG C, and the polymerization reaction time is 3~9h.Under specified conditions of the invention, vinyl monomer It can mutually polymerize, assign leather excellent filling effect, increase leather is plentiful, grain compactibility and water-fastness and waterproofness etc.; Meanwhile first intermediate, the second intermediate and vinyl monomer mutually polymerize, finally obtained greasing-retanning agnt of leather is soft Property, richness and uniformity are preferable.
Present invention preferably employs such as under type to carry out performance measurement to the greasing-retanning agnt of leather being prepared:
Heat-resistant stability detection:In 50 degree of baking ovens, places 15 days and observe;
Acid-resistant stability detection:Using 1:1:8 ratio, 10 parts of greases, 10 part 10% of sulfuric acid liquid, 80 parts of deionization Water, 4 hours, observation is layered and precipitation status;
Osmotic evenness, pliability and surface feel, fillibility, fullness:Using sensory evaluation:Randomly select 10 systems Leather technical staff evaluates, and standards of grading use ten point system, 10 points to be best, 1 point is worst;
Grease resistance extracting property detection:QBT 2718-2005;
Waste liquid COD detection:QB 11914-89
In order to further illustrate the present invention, greasing-retanning agnt of leather provided by the invention is carried out with reference to embodiments detailed Thin description.
Embodiment 1
In glass reactor, be added 1.0mol 12, tetradecyl alchohol, the maleic anhydride of 1.0mol is added, in 85 DEG C of items Under part, esterification 3.5 hours;Generate 12, tetradecyl alchohol maleic anhydride monoesters, the first intermediate of as 1mol;
In glass reactor, 1.0mol rapeseed oil is added, the diethanol amine of 1.0mol is added, under the conditions of 125 DEG C, amine Change reaction 3.5 hours, generates polyol;80 DEG C of cooling, is added the maleic anhydride of 1.0mol, is warming up to 115 DEG C, reaction 2.5 hours, generate maleate, the second intermediate of as 1mol;
In high-pressure glass reactor, about 600 grams of deionized water are added, 3.5 grams of lauryl sodium sulfate, is added The first intermediate of 0.25mol, the second intermediate of 0.25mol;125 DEG C of heating;It is spare;
Potassium peroxydisulfate is made into 80 grams of aqueous solution of 2%, it is spare;By the acrylic acid of 1.0mol, the metering system of 1.0mol Acid adds the deionized water of 0.2mol to dilute spare;
In 3 hours, by potassium peroxydisulfate dilution and the mixed liquor of acrylic acid and methacrylic acid, it is added drop-wise to contains respectively In the reactor for having the first intermediate and the second intermediate, after completion of dropwise addition, heats up 130 DEG C, keep the temperature 1.5 hours;45 DEG C of cooling Hereinafter, 335 gram 30% of sodium hydroxide solution and 310 grams of deionized water is added dropwise, obtaining pH value is 6.30, solid content 33.5% Greasing-retanning agnt of leather.
Embodiment 2
In glass reactor, be added 0.5mol 16, octadecyl alcolol, the maleic anhydride of 0.5mol is added, in 85 DEG C of items Under part, esterification 3.5 hours;Generate 16, octadecyl alcolol maleic anhydride monoesters, the first intermediate of as 0.5mol;
In glass reactor, 0.5mol rapeseed oil is added, the diethanol amine of 0.5mol is added, under the conditions of 125 DEG C, amine Change reaction 3.5 hours, generates polyol;80 DEG C of cooling, is added the maleic anhydride of 0.5mol, is warming up to 120 DEG C, reaction 2.5 hours, generate maleate, as the second intermediate of 0.5mol;
In high-pressure glass reactor, about 500 grams of deionized water are added, 2.0 grams of lauryl sodium sulfate, is added The first intermediate of 0.20mol, the second intermediate of 0.20mol;125 DEG C of heating;It is spare;
Potassium peroxydisulfate is made into 50 grams of aqueous solution of 2%, it is spare;By the acrylic acid of 0.3mol, the metering system of 0.3mol Acid adds the deionized water of 0.06mol to dilute spare;
In 3 hours, by potassium peroxydisulfate dilution and the mixed liquor of acrylic acid and methacrylic acid, it is added drop-wise to contains respectively In the reactor for having the first intermediate and the second intermediate, after completion of dropwise addition, heats up 130 DEG C, keep the temperature 1.5 hours;45 DEG C of cooling Hereinafter, appropriate 133 gram 30% of sodium hydroxide solution and the deionized water of 50g is added dropwise, pH value 6.10 is obtained, solid content 32% Greasing-retanning agnt of leather.
Embodiment 3
In glass reactor, be added 1.0mol 12, tetradecyl alchohol, the maleic anhydride of 1.0mol is added, in 85 DEG C of items Under part, esterification 3.5 hours;Generate 12, tetradecyl alchohol maleic anhydride monoesters, the first intermediate of as 1mol;
In glass reactor, 1.0mol neat's foot oil is added, the diethanol amine of 1.0mol is added, under the conditions of 125 DEG C, amine Change reaction 3.5 hours, generates polyol;80 DEG C of cooling, is added the maleic anhydride of 1.0mol, is warming up to 115 DEG C, reaction 2.5 hours, generate maleate, the second intermediate of as 1mol;
In high-pressure glass reactor, about 600 grams of deionized water are added, 3.5 grams of lauryl sodium sulfate, is added The first intermediate of 0.25mol, the second intermediate of 0.25mol;125 DEG C of heating;It is spare;
Potassium peroxydisulfate is made into 80 grams of aqueous solution of 2%, it is spare;By the acrylic acid of 1.5mol, the acrylonitrile of 0.5mol adds The deionized water dilution of 0.2mol is spare;
In 3 hours, potassium peroxydisulfate dilution and acrylic acid and the mixed liquor of acrylonitrile are added drop-wise to respectively containing In the reactor of one intermediate and the second intermediate, after completion of dropwise addition, heats up 130 DEG C, keep the temperature 1.5 hours;Cooling 45 DEG C hereinafter, 266 gram 30% of sodium hydroxide solution and 40g deionized water is added dropwise, obtaining pH value is 6.70, and the leather of solid content 34.5% adds Rouge retanning agent.
Embodiment 4
In glass reactor, be added 1.0mol 16, octadecyl alcolol, the maleic anhydride of 1.0mol is added, in 85 DEG C of items Under part, esterification 3.5 hours;Generate 16, octadecyl alcolol maleic anhydride monoesters, the first intermediate of as 1mol;
In glass reactor, 1.0mol neat's foot oil is added, the diethanol amine of 1.0mol is added, under the conditions of 125 DEG C, amine Change reaction 3.5 hours, generates polyol;80 DEG C of cooling, is added the maleic anhydride of 1.0mol, is warming up to 115 DEG C, reaction 2.5 hours, generate maleate, the second intermediate of as 1mol;
In high-pressure glass reactor, about 600 grams of deionized water are added, 3.5 grams of lauryl sodium sulfate, is added The first intermediate of 0.25mol, the second intermediate of 0.25mol;125 DEG C of heating;It is spare;
Potassium peroxydisulfate is made into 80 grams of aqueous solution of 2%, it is spare;By the acrylic acid of 0.25mol, the methyl-prop of 0.25mol Olefin(e) acid adds the deionized water of 0.05mol to dilute spare;
In 3 hours, by potassium peroxydisulfate dilution and the mixed liquor of acrylic acid and methacrylic acid, it is added drop-wise to contains respectively In the reactor for having the first intermediate and the second intermediate, after completion of dropwise addition, heats up 130 DEG C, keep the temperature 1.5 hours;45 DEG C of cooling Hereinafter, 134 gram 30% of sodium hydroxide solution and the deionized water of 35g is added dropwise, pH value 6.25, the skin of solid content 33.5% are obtained Remove from office lubricating retanning agent.
Embodiment 5
In glass reactor, be added 1.0mol 16, octadecyl alcolol, the maleic anhydride of 1.0mol is added, in 85 DEG C of items Under part, esterification 3.5 hours;Generate 16, octadecyl alcolol maleic anhydride monoesters, the first intermediate of as 1mol;
In glass reactor, 1.0mol castor oil is added, the ethanol amine of 1.0mol is added, under the conditions of 125 DEG C, amination Reaction 3.5 hours generates polyol;80 DEG C of cooling, is added the maleic anhydride of 1.0mol, is warming up to 115 DEG C, reaction 2.5 hours, generate maleate, the second intermediate of as 1mol;
In high-pressure glass reactor, about 600 grams of deionized water are added, 2.5 grams of lauryl sodium sulfate, is added The first intermediate of 0.30mol, the second intermediate of 0.25mol;125 DEG C of heating;It is spare;
Potassium peroxydisulfate is made into 80 grams of aqueous solution of 2%, it is spare;By the acrylic acid of 0.25mol, the methyl-prop of 0.25mol Olefin(e) acid adds the deionized water of 0.05mol to dilute spare;
In 3 hours, by potassium peroxydisulfate dilution and the mixed liquor of acrylic acid and methacrylic acid, it is added drop-wise to contains respectively In the reactor for having the first intermediate and the second intermediate, after completion of dropwise addition, heats up 130 DEG C, keep the temperature 1.5 hours;45 DEG C of cooling Hereinafter, 134 gram 30% of sodium hydroxide solution and the deionized water of 40g is added dropwise, pH value 6~7, the leather of solid content 33% are obtained Lubricating retanning agent.
Embodiment 6
In glass reactor, the PPG200 of 1.0mol is added, the maleic anhydride of 1.0mol is added, under the conditions of 85 DEG C, Esterification 3.5 hours;Generate PPG200 maleic anhydride monoesters, the first intermediate of as 1mol;
In glass reactor, 1.0mol neat's foot oil is added, the diethanol amine of 1.0mol is added, under the conditions of 125 DEG C, amine Change reaction 3.5 hours, generates polyol;80 DEG C of cooling, is added the maleic anhydride of 1.0mol, is warming up to 115 DEG C, reaction 2.5 hours, generate maleate, the second intermediate of as 1mol;
In high-pressure glass reactor, about 600 grams of deionized water are added, 3.5 grams of lauryl sodium sulfate, is added The first intermediate of 0.25mol, the second intermediate of 0.25mol;125 DEG C of heating;It is spare;
Potassium peroxydisulfate is made into 80 grams of aqueous solution of 2%, it is spare;By the acrylic acid of 0.75mol, the methyl-prop of 0.25mol Olefin(e) acid adds the deionized water of 0.1mol to dilute spare;
In 3 hours, by potassium peroxydisulfate dilution and the mixed liquor of acrylic acid and methacrylic acid, it is added drop-wise to contains respectively In the reactor for having the first intermediate and the second intermediate, after completion of dropwise addition, heats up 130 DEG C, keep the temperature 1.5 hours;45 DEG C of cooling Hereinafter, 200 gram 30% of sodium hydroxide solution and the deionized water of 40g is added dropwise, pH value 6.55,33.5% leather of solid content are obtained Lubricating retanning agent.
Comparative example 1
Take industrial rape oil 2.0kg, with ethanol amine 0.6kg at 125 DEG C ester exchange reaction 2 hours, add maleic anhydride 1.0kg,
The reaction was continued 2 hours, obtains grease performed polymer containing double bonds;With sodium hydroxide solution by the pH of above-mentioned performed polymer Value is adjusted to 7.5.
Static 0.5 hour, heating was added at one time 1% ammonium persulfate solution 1.0kg under stiring, drips in 2 hours Add 0.7kg acrylic acid, wherein 80 DEG C polymerization reaction 3 hours, be warming up to 85 DEG C of polymerization reactions 1 hour, cooling reaction product is extremely Room temperature obtains the greasing-retanning agnt of leather of solid content 30%.
Embodiment 7
Take shaving blue wet yak leather:1.0~1.2mm of thickness, weighing;
Rewetting:Liquor ratio 300;0.5%DOWELLAN HS;0.5% oxalic acid;45℃;90min;Control water, 300% water, water Wash 10min;
It neutralizes:150% water, 35 DEG C, 2% DOWELLTAN NL20,1% sodium formate, 20min;0.5% little Su It beats, 60min, adjusts pH value 5.0 or so;300% washing, 10*2min;
Retanning filling:Liquor ratio 100%, room temperature, 3%RV13,3%DD42,15% Examples 1 to 6 and comparative example 1, 90min;0.5% formic acid:10min;0.5% formic acid:20min;PH value about 4.5 or so;Control water;
Stuffing:55 degree of moisturizing, liquor ratio:150 5%FS-85,90min;2.0% formic acid, is added in three times, interval 20min;Adjust ph3.5~3.6;
Then , Shi Bandages plate, drying are washed, rewetting is fallen soft.
Performance test:
By Examples 1 to 6 and comparative example 1, technique is compared as described above and carries out leather retanning stuffing test;Wherein have Stuffing, for the polymer of retanning with the weight fraction of shaving wet blue leather for 15%, above-mentioned leather compares main material used in technique It is Da Wei joint-stock company production material;With comparative example 1 as object of reference, skin bit comparative test is carried out;And detected respectively, Its performance is as shown in table 1, and table 1 is the embodiment of the present invention 1~6 and 1 performance measurement result of comparative example.
1 embodiment of the present invention 1~6 of table and 1 performance measurement result of comparative example
As can be seen from Table 1, polymer made from Examples 1 to 6 all has good osmotic evenness, pliability, pole Good plentiful filling effect, splendid surface feel;Soft in stability for Examples 1 to 6, infiltration is plentiful It is significantly better than comparative example 1;The polymer is embodied with apparent application effect and application performance.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered It is considered as protection scope of the present invention.

Claims (10)

1. a kind of preparation method of greasing-retanning agnt of leather, which is characterized in that include the following steps:
A) alcohols reacts to obtain the first intermediate with maleic anhydride;
Aminated compounds of the natural oil through hydroxyl is modified, obtains the compound of hydroxyl;The compound of the hydroxyl and horse Carry out anhydride reaction, obtains the second intermediate;
B) first intermediate, the second intermediate and vinyl monomer are under the action of reaction medium, emulsifier and initiator Polymerization reaction occurs, obtains greasing-retanning agnt of leather;The polymeric reaction temperature is 120~160 DEG C, the polymerization reaction time For 3~9h.
2. preparation method according to claim 1, which is characterized in that the step B) reaction medium be water.
3. preparation method according to claim 1, which is characterized in that the vinyl monomer is that the mode being added dropwise is added, Time for adding is 2~6h.
4. preparation method according to claim 1, which is characterized in that the vinyl monomer is selected from acrylicacidandesters One of class, oleic acid vinyl acetate, vinylacetate, styrene, acrylonitrile and acrylamide are a variety of.
5. preparation method according to claim 1, which is characterized in that the initiator is selected from ammonium persulfate, sodium peroxydisulfate One or more of with potassium peroxydisulfate.
6. preparation method according to claim 1, which is characterized in that the alcohols can be cell alcohol or polyalcohol;Institute State one kind or more that cell alcohol is selected from ethyl alcohol, butanol, isooctanol, the fatty alcohol of C12~14, the fatty alcohol of C16~18 and C20 fatty alcohol Kind;The polyalcohol is selected from one of dihydric alcohol and trihydroxylic alcohol or a variety of.
7. preparation method according to claim 1, which is characterized in that the molar ratio of the alcohols and maleic anhydride be (1~ 2):1.
8. preparation method according to claim 1, which is characterized in that the natural oil is in vegetable oil and animal oil It is one or more.
9. preparation method according to claim 1, which is characterized in that the aminated compounds of the hydroxyl is selected from ethyl alcohol Amine, diethanol amine and triethanolamine it is one or more.
10. a kind of greasing-retanning agnt of leather, which is characterized in that prepared by preparation method described in any one of claim 1 to 9 It obtains.
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