CN109706275A - The preparation method of siliceous tanning agent, siliceous tanning agent and application - Google Patents
The preparation method of siliceous tanning agent, siliceous tanning agent and application Download PDFInfo
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Abstract
The present invention provides a kind of preparation method of siliceous tanning agent, siliceous tanning agent and applications, are related to leather technology field, and the preparation method by obtaining the siliceous tanning agent for esters of silicon acis, silane coupling agent, bleeding agent, water and cosolvent after mixing.Wherein esters of silicon acis is silicon source presoma, and silane coupling agent is organic modifiers, can finally generate the improved silica containing more active group, can be with collagen strong effect.And the penetrating power for increasing siliceous tanning agent by compounding bleeding agent, can be effectively improved the shrinkage temperature, tensile strength, tearing strength of finished leather.This method also have it is easy to operate, to production equipment without specific demand, the advantages of being suitble to large-scale production.
Description
Technical field
The present invention relates to leather technology fields, more particularly, to a kind of preparation method of siliceous tanning agent, siliceous tanning agent and answer
With.
Background technique
Chrome tanning legal system skin is the main stream approach of current leather industry, and leather made from this method is often in blue-green, and chromium
Utilization rate of the powder in tannery is lower, and a large amount of unreacted chromium powders endanger water body resource with discharge of wastewater, causes environment dirty
Dye.With the reinforcement of environment and resources consciousness and the appearance of many global environmental problems, " sustainable development ", " greenization
Learn ", the concepts such as " environmentally-friendly technique " and " cleanly production " are gradually rooted in the hearts of the people.A kind of shallow white leathers of energy manufacture, and
Become the focus on research direction of vast process hides worker conducive to the chrome-free tanning agent of environmental protection.
Currently, having already appeared a series of chrome-free tanning agent in the market by domestic and foreign scholars' persevering endeavors.But
It is that the shrinkage temperature of the leather of these chrome-free tanning agent tannings is lower, the performance and quality of leather have to be hoisted, and its waste liquid and tan
A certain amount of harmful substance can be remained in the leather of system.
For example, the method for studying more related no chrome tanning material both at home and abroad is using glutaraldehyde, modified glutaraldehyde to skin
Leather carries out pre-tanning, main tan.In addition, forming modified phosphonium salt compound-organic phosphorus tanning agent by the concentrate and additive of phenol is also
The focus on research direction of research worker.
There is within 1862 scholar's discovery that can precipitate gelatin using silicic acid, illustrating can phase interaction between silicic acid and collagenous fibres
With crosslinking.Existing silicon class tanning agent permeability in the tanning of early period is poor, easily in conjunction with skin excessive surface, is unfavorable for into
The uniform tanning of leather.The ethyl orthosilicate tanning hide using modified grease as dispersible carrier exists in the prior art, finished leather
Shrinkage temperature has certain promotion, and each functional.But process for tanning needs to carry out water squeezing processing to skin, does not meet industry and wants
It asks, the auxiliary that shrinkage temperature is also required to other tanning agents gets to require.Therefore, it is further improved the preparation method of siliceous tanning agent
The problem of being current urgent need to resolve.
In view of this, the present invention is specifically proposed.
Summary of the invention
The first object of the present invention is to provide a kind of preparation method of siliceous tanning agent, and the preparation method is environmental-friendly, behaviour
Make simple, the siliceous tanning agent good penetrability being prepared, and can effectively improve the performance of finished leather.
The second object of the present invention is to provide a kind of siliceous tanning agent being prepared using above-mentioned preparation method, this is siliceous
Tanning agent can effectively improve the shrinkage temperature, tensile strength and tearing strength of finished leather.
The third object of the present invention is to provide application of the above-mentioned siliceous tanning agent of one kind in leather arrangement.
In order to solve the above technical problems, spy of the present invention adopts the following technical scheme that
A kind of preparation method of siliceous tanning agent, esters of silicon acis, silane coupling agent, bleeding agent, water and cosolvent are uniformly mixed
After obtain the siliceous tanning agent.
Preferably, first water and bleeding agent are mixed, is then adjusted to neutrality the pH of system, esters of silicon acis, silicon is then added
Alkane coupling agent and cosolvent, maintaining mixed system temperature is 50-70 DEG C, obtains the siliceous tanning agent after mixing evenly.
Preferably, pH adjusting is carried out by the way that pH adjusting agent is added；
Wherein, the pH adjusting agent includes potassium hydroxide, sodium hydroxide or ammonium hydroxide, preferably sodium hydroxide；
Preferably, pH to 6.5-7.5 is adjusted.
Preferably, the silane coupling agent is Y (CH2)nSiX3；
Wherein, Y is hydrogen, vinyl, epoxy group, amino, methacryloxy or urea groups；X is halogen, methoxyl group, second
Oxygroup or acetoxyl group；The integer of n=0-3；
Preferably, Y is hydrogen, vinyl or epoxy group；X is methoxy or ethoxy；The integer of n=0-3；
It is highly preferred that the silane coupling agent is methyltriethoxysilane.
Preferably, the esters of silicon acis includes methyl orthosilicate, ethyl orthosilicate, positive silicic acid propyl ester；It is preferred that the silicic acid second that is positive
Ester.
Preferably, the cosolvent is C1-C8 low-carbon alcohols；
Preferably, the C1-C8 low-carbon alcohols include methanol, ethyl alcohol, propyl alcohol or amylalcohol, more preferably ethyl alcohol.
Preferably, the bleeding agent is mainly reacted to obtain sulfonated castor oil with sulfonating agent by castor oil；
Preferably, it reacts 100-120 parts of castor oil and 10-35 parts of sulfonating agent to obtain sulfonated castor oil；
Preferably, sulfonating agent is sulfuric acid；
Preferably, the sulfonated castor oil is made by the following method: being added dropwise under conditions of 25-35 DEG C into castor oil
Sulfuric acid, the time that sulfuric acid is added dropwise are no more than 3 hours；And reacting when the oil liquid of castor oil is dark green terminates, and then uses
The sodium chloride solution 5-20 parts by weight that concentration is 5%-15% wash oil liquid.
Preferably, in parts by weight, the raw material to prepare siliceous tanning agent is as follows for number: 15-35 parts of esters of silicon acis, silicon
15-35 parts of alkane coupling agent, 110-155 parts of bleeding agent, 1-5 parts of water and 1-5 parts of cosolvent；
It is highly preferred that number is in parts by weight, the raw material to prepare siliceous tanning agent is as follows: 18-30 parts of esters of silicon acis,
18-30 parts of silane coupling agent, 120-145 parts of bleeding agent, 1-4 parts of water and 1-4 parts of cosolvent；
It is further preferred that number is in parts by weight, the raw material to prepare siliceous tanning agent is as follows: esters of silicon acis 20-
25 parts, 20-25 parts of silane coupling agent, 128-137 parts of bleeding agent, 2-3 parts of water and 2-3 parts of cosolvent；
Preferably, the raw material to prepare siliceous tanning agent further includes 5-35 parts of pH adjusting agent, preferably 10-30 parts, more excellent
It is selected as 20-25 parts.
The present invention also provides a kind of siliceous tanning agents that above-mentioned preparation method is prepared.
The present invention also provides a kind of application of above-mentioned siliceous tanning agent in leather arrangement.
Compared with prior art, the invention has the following beneficial effects:
The preparation method of siliceous tanning agent provided by the invention, by esters of silicon acis, silane coupling agent, bleeding agent, water and cosolvent
The siliceous tanning agent is obtained after mixing.The preparation method is organic with silane coupling agent using esters of silicon acis as silicon source presoma
Modifying agent can finally generate the improved silica containing more active group.It is strong with collagen effect, can effectively change
Shrinkage temperature, tensile strength, the tearing strength of kind finished leather.And siliceous tanning agent provided by the invention does not contain metal ion, because
This has the advantages of environmental-friendly when use, not cause water pollution.And the siliceous tanning agent has preferable permeability,
The uniform tanning hide of energy, tanned leather is white, the tanning suitable for Bai Pi and light skin；The preparation method environment
Close friend does not discharge environmentally harmful waste during preparation；This method is easy to operate, to production equipment without special need
It asks, is suitble to large-scale production.The siliceous tanning agent provided by the invention being prepared using above-mentioned preparation method, it may have above-mentioned to have
Beneficial effect.
The present invention also provides application of the above-mentioned siliceous tanning agent in leather arrangement, above-mentioned siliceous tanning agent is used for tanning skin
Leather, can effectively improve the shrinkage temperature, tensile strength and tearing strength of finished leather.And the above-mentioned tanned leather of siliceous tanning agent is in
White, therefore can be applied to the white skin of tanning and light skin.
Specific embodiment
Technical solution of the present invention is clearly and completely described below in conjunction with embodiment, it is clear that described reality
Applying example is a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field
Art personnel every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.The person that is not specified actual conditions in embodiment, carries out according to conventional conditions or manufacturer's recommended conditions.Agents useful for same or instrument
Production firm person is not specified, is the conventional products that can be obtained by commercially available purchase.
The present invention provides a kind of preparation method of siliceous tanning agent, the preparation method by by esters of silicon acis, silane coupling agent,
Bleeding agent, water and cosolvent obtain the siliceous tanning agent after mixing.Tanning agent is that one kind has multi-functional active material,
At least contain two or more functional groups in its molecular structure.Tanning agent can be with two or more in collagen structure
Position form intramolecular bond, while a part of intramolecular bond in collagen can be destroyed, and generate more new intermolecular friendships
Connection, and there is tanning effect.
The preparation method of siliceous tanning agent provided by the invention is to have with silane coupling agent using esters of silicon acis as silicon source presoma
Machine modifying agent can finally generate the improved silica containing more active group.With water hydrolysis-condensation can occur for esters of silicon acis
Reaction, reaction can obtain having certain degree of polymerization, silica solution of the surface rich in hydroxyl.There is ammonia on materials with hide glue fibril side chain
Base, carboxyl isoreactivity group, silica solution have the group that hydrogen bond is formed with active group on collagen.Further, by
The bonded combination silane coupling agent of silica surface, to reach having in the inorganic interface of silica and ox-hide collagen
The purpose of bonding is formed between machine interface, it is further to promote to form molecule with positions two or more in collagen structure
Internal key.Therefore, the preparation method of siliceous tanning agent provided by the invention is with silane coupling agent using esters of silicon acis as silicon source presoma
Organic modifiers can finally generate the improved silica containing more active group.It is strong with collagen effect, can have
Effect improves shrinkage temperature, tensile strength, the tearing strength of finished leather.And siliceous tanning agent provided by the invention without containing metal from
Son, therefore there is the advantages of environmental-friendly when use, not cause water pollution；The siliceous tanning agent has preferable infiltration
Property, the uniform tanning hide of energy, tanned leather is white, the tanning suitable for Bai Pi and light skin；The preparation method
It is environmental-friendly, environmentally harmful waste is not discharged during preparation；The preparation method is easy to operate, to production equipment without
Specific demand is suitble to large-scale production.
In the preparation method of siliceous tanning agent provided by the invention, the raw material used includes esters of silicon acis, silane coupling agent, infiltration
Saturating agent, water and cosolvent.
In some alternative embodiments, the esters of silicon acis includes methyl orthosilicate, ethyl orthosilicate, positive silicic acid third
Ester, preferably ethyl orthosilicate.It, can be more fully compound with organic phase when the source of silica is ethyl orthosilicate.When just
Silicate hydrolyzate and condensation, with organic monomer polymerize carry out simultaneously when, linear organic polymer backbones and three can be formed
Network of silica half interpenetrating network structure is tieed up, reaches the compound of molecular level, phase separation degree is small.Optionally, raw material includes
15-35 parts of esters of silicon acis, such as can be but be not limited to 15 parts, 17 parts, 20 parts, 22 parts, 24 parts, 25 parts, 26 parts, 28 parts, 30
Part, 33 parts or 35 parts.
In some alternative embodiments, the silane coupling agent is Y (CH2)nSiX3；Wherein, Y be hydrogen, vinyl,
Epoxy group, amino, methacryloxy or urea groups；X is halogen, methoxyl group, ethyoxyl or acetoxyl group；N=0-3's is whole
Number.In some preferred embodiments, Y is hydrogen, vinyl or epoxy group；X is methoxy or ethoxy；N=0-3's is whole
Number；In some preferred embodiments, the silane coupling agent is methyltriethoxysilane.The present invention passes through experiment hair
It is existing, optimize the selection of group in silane coupling agent, tanning agent can be optimized to the effect of leather tannin, wherein with methyl triethoxy
Silane, can the better shape between the inorganic interface of silica and the organic interface of the collagen of ox-hide as coupling agent
At bonding, promote to form intramolecular bond with positions two or more in collagen structure.Optionally, raw material includes silicon
Alkane coupling agent 15-35 parts by weight, such as can be but be not limited to 15 parts, 17 parts, 20 parts, 22 parts, 24 parts, 25 parts, 26 parts, 28
Part, 30 parts, 33 parts or 35 parts.
The effect of bleeding agent is emulsification esters of silicon acis and silane coupling agent, and bleeding agent itself is free of and esters of silicon acis and silane coupled
The active group of agent reaction.Because rawhide has certain hydrophobicity, become super hydrophilic orthosilicic acid or poly after silicic acid ester hydrolysis
Silicic acid needs to be added at this time the silane coupling agent containing hydrophobic grouping and helps its infiltration, after infiltration again by way of mentioning alkali
React the active group of silica tanning agent with the active group of collagen.
In some alternative embodiments, the bleeding agent for example can be but be not limited to sulfonated castor oil, alkyl
Sodium sulfonate, sodium alkyl benzene sulfonate, alkyl sulfate sodium, sodium secondary alkyl sulfonate, secondary alkyl sulphate sodium, mono- sodium olefin sulfonate of α, alkane
Base sodium naphthalene sulfonate, succinic acid alkyl ester sulfonate sodium, Igepon T, sulfamic acid sodium, fatty alcohol polyoxyethylene ether, alkyl phenol polyoxy
Vinethene, polyethers, phosphate compounds and ketone or ethers bleeding agent etc..
In some preferred embodiments, when using sulfonated castor oil as bleeding agent, the osmotic effect of siliceous tanning agent
More preferably.Optionally, raw material includes bleeding agent 110-155 parts, such as can be but be not limited to 110 parts, 115 parts, 120 parts, 125
Part, 130 parts, 135 parts, 140 parts, 145 parts, 150 parts or 155 parts.
Sulfonated castor oil can be improved the emulsification penetrating power of siliceous tanning agent, when it is dispersed in dispersate surface, be formed
Film or electric double layer can make dispersed phase with charge, the droplet of dispersed phase can be prevented to condense mutually, the emulsion of formation compares
Stablize, the siliceous tanning agent layering avoided.Meanwhile with hydrophilic and oleophylic characteristic, make each component of siliceous tanning agent
It is more uniform, it is more easier to penetrate into leather, keeps the tannin effect of siliceous tanning agent more preferable.
Esters of silicon acis can occur hydrolysis-condensation with water and react, and reaction can obtain having certain degree of polymerization, surface rich in hydroxyl
The silica solution of base, therefore preparing for siliceous tanning agent needs water in raw material, keep esters of silicon acis molten by hydrolysis-condensation reaction generation silicon
Glue.Optionally, raw material includes water 1-5 parts, such as can be but be not limited to 1 part, 2 parts, 3 parts, 4 parts or 5 parts.
The cosolvent of water and esters of silicon acis is also needed to promote to react homogeneous stability progress in reaction raw materials.Optionally, described total
Solvent is C1-C8 low-carbon alcohols；Preferably, the C1-C8 low-carbon alcohols include methanol, ethyl alcohol, propyl alcohol or amylalcohol, more preferably second
Alcohol.Optionally, raw material includes cosolvent 1-5 parts, such as can be but be not limited to 1 part, 2 parts, 3 parts, 4 parts or 5 parts.
In some preferred embodiments, in parts by weight, as follows to prepare the raw material of siliceous tanning agent: silicic acid
18-30 parts of ester, 18-30 parts of silane coupling agent, 120-145 parts of bleeding agent, 1-4 parts of water and 1-4 parts of cosolvent.
In some preferred embodiments, in parts by weight, the raw material to prepare siliceous tanning agent is as follows: silicon
20-25 parts of acid esters, 20-25 parts of silane coupling agent, 128-137 parts of bleeding agent, 2-3 parts of water and 2-3 parts of cosolvent.By further
The formula ratio for optimizing each raw material can further optimize the tanning performance of siliceous tanning agent.
In some alternative embodiments, the preparation method includes first mixing water and bleeding agent, then by system
PH be adjusted to neutrality, esters of silicon acis, silane coupling agent and cosolvent is then added, maintaining mixed system temperature is 50-70
DEG C, the siliceous tanning agent is obtained after mixing evenly.
In some preferred embodiments, the preparation method of above-mentioned siliceous tanning agent carries out in accordance with the following steps:
A) castor oil is added in reaction kettle, sulfuric acid is slowly added dropwise while stirring, 25-35 DEG C of reaction temperature, sulfuric acid will be 3
It is added in hour.Reaction observes oil liquid color after carrying out at least 2 hours, indicates that sulfonating reaction terminates if dark green.
B) oil liquid first is washed using the sodium chloride solution 5-20 parts by weight that concentration is 5%-15%, takes upper layer after stratification
Oil liquid, and pH adjusting agent and water are added in oil liquid, oil liquid terminal pH is 6.5-7.5.
C) oil liquid after neutralizing, esters of silicon acis, silane coupling agent and the cosolvent of formula ratio, under conditions of 50-70 DEG C are taken
It stirs evenly and obtains siliceous tanning agent.
In some alternative embodiments, the dosage of castor oil is 100-120 parts by weight in sulfonating reaction, such as can be
But 100 parts, 102 parts, 105 parts, 108 parts, 110 parts, 112 parts, 115 parts, 117 parts, 118 parts or 120 parts are not limited to, preferably
It is 105-115 parts, 108-112 parts more preferable；The dosage of sulfonating agent is 10-35 parts by weight in sulfonating reaction, such as can be but not
Be limited to for for example can be but be not limited to 10 parts, 12 parts, 15 parts, 17 parts, 20 parts, 22 parts, 24 parts, 25 parts, 26 parts, 28 parts,
It is 30 parts, 33 parts or 35 parts, preferably 15-30 parts, 20-25 parts more preferable.Optionally, sulfuric acid can also be other sulphurs in above-mentioned reaction
Agent, such as can be but be not limited to chlorosulfonic acid or sulfur trioxide, sulfonating agent is preferably sulfuric acid in above-mentioned reaction.
In some alternative embodiments, the reaction temperature of sulfonating reaction is 20-35 DEG C, such as can be but be not limited to
20 DEG C, 21 DEG C, 22 DEG C, 23 DEG C, 24 DEG C, 25 DEG C, 26 DEG C, 27 DEG C, 28 DEG C, 29 DEG C, 30 DEG C, 32 DEG C or 35 DEG C；It is preferred that 28-32
DEG C, more preferable 30 DEG C.
In some alternative embodiments, the concentration of sodium chloride solution is 5%-15%, such as can be but be not limited to
It is 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14% or 15%, preferred concentration 8%-12%.
In some alternative embodiments, the dosage of sodium chloride solution is 5-20 parts by weight, such as can be but unlimited
In being 5 parts, 7 parts, 8 parts, 10 parts, 12 parts, 14 parts, 15 parts, 16 parts, 18 parts or 20 parts, preferably 10-12 parts.
In some alternative embodiments, the dosage of pH adjusting agent is 5-35 parts by weight, such as can be but be not limited to
It is 5 parts, 10 parts, 12 parts, 15 parts, 17 parts, 20 parts, 22 parts, 24 parts, 25 parts, 26 parts, 28 parts, 30 parts or 35 parts；Preferably 10-
30 parts, more preferably 20-25 parts.In some alternative embodiments, pH adjusting agent includes potassium hydroxide, sodium hydroxide or ammonia
Water, preferably sodium hydroxide.
In some alternative embodiments, temperature condition when each raw material stirs and evenly mixs in step c) is 50-70 DEG C, example
It such as can be but be not limited to 50 DEG C, 52 DEG C, 55 DEG C, 58 DEG C, 60 DEG C, 62 DEG C, 65 DEG C, 67 DEG C or 70 DEG C.
By adjusting each technological parameter in optimization above-mentioned steps, the tannin effect of siliceous tanning agent can be further adjusted and optimized
Fruit.
The present invention also provides a kind of siliceous tanning agent that above-mentioned preparation method is prepared, the siliceous tanning agent with it is above-mentioned siliceous
The preparation method of tanning agent is based on identical inventive concept, therefore all beneficial effects with above-mentioned preparation method, herein no longer
It repeats.
The present invention also provides application of the above-mentioned siliceous tanning agent in leather arrangement, above-mentioned siliceous tanning agent is used for tanning skin
Leather, can effectively improve the shrinkage temperature, tensile strength, tearing strength of finished leather.And the above-mentioned tanned leather of siliceous tanning agent is in
White, therefore can be applied to the tanning of the white skin of tanning and light skin.
Beneficial effects of the present invention are further illustrated below with reference to preferred embodiment.
Embodiment 1
A kind of preparation method of siliceous tanning agent is present embodiments provided, according to parts by weight includes the following raw material: positive silicic acid
22 parts of ethyl ester, 22 parts of methyltriethoxysilane, 135 parts of sulfonated castor oil, 2.5 parts of water and 2.5 parts of ethyl alcohol.
The preparation method of above-mentioned siliceous tanning agent carries out in accordance with the following steps:
A) 110 parts by weight castor oil are added in reaction kettle, 25 parts sulfuric acids, reaction temperature is slowly added dropwise while stirring
30 DEG C, sulfuric acid will add in 3 hours.Reaction observes oil liquid color after carrying out at least 2 hours, and sulfonation is indicated if dark green
Reaction terminates.
B) oil liquid first is washed using 12 parts by weight of sodium chloride solution that concentration is 10%, takes upper layer oil liquid after stratification,
And water and 22 parts by weight of sodium hydroxide are added in oil liquid, oil liquid terminal pH is 6.5-7.5.
C) oil liquid after neutralizing, ethyl orthosilicate, methyltriethoxysilane and the ethyl alcohol of formula ratio, in 60 DEG C of item are taken
It is stirred evenly under part and obtains siliceous tanning agent.
Embodiment 2
A kind of preparation method of siliceous tanning agent is present embodiments provided, according to parts by weight includes the following raw material: positive silicic acid
20 parts of ethyl ester, 25 parts of methyltriethoxysilane, 128 parts of sulfonated castor oil, 3 parts of water and 2 parts of ethyl alcohol.
The preparation method of above-mentioned siliceous tanning agent carries out in accordance with the following steps:
A) 108 parts by weight castor oil are added in reaction kettle, 20 parts sulfuric acids, reaction temperature is slowly added dropwise while stirring
32 DEG C, sulfuric acid will add in 3 hours.Reaction observes oil liquid color after carrying out at least 2 hours, and sulfonation is indicated if dark green
Reaction terminates.
B) oil liquid first is washed using 10 parts by weight of sodium chloride solution that concentration is 12%, takes upper layer oil liquid after stratification,
And water and 25 parts by weight of sodium hydroxide are added in oil liquid, oil liquid terminal pH is 6.5-7.5.
C) oil liquid after neutralizing, ethyl orthosilicate, methyltriethoxysilane and the ethyl alcohol of formula ratio, in 65 DEG C of item are taken
It is stirred evenly under part and obtains siliceous tanning agent.
Embodiment 3
A kind of preparation method of siliceous tanning agent is present embodiments provided, according to parts by weight includes the following raw material: positive silicic acid
25 parts of ethyl ester, 20 parts of methyltriethoxysilane, 137 parts of sulfonated castor oil, 2 parts of water and 3 parts of ethyl alcohol.
The preparation method of above-mentioned siliceous tanning agent carries out in accordance with the following steps:
A) 112 parts by weight castor oil are added in reaction kettle, 25 parts sulfuric acids, reaction temperature is slowly added dropwise while stirring
28 DEG C, sulfuric acid will add in 3 hours.Reaction observes oil liquid color after carrying out at least 2 hours, and sulfonation is indicated if dark green
Reaction terminates.
B) oil liquid first is washed using 15 parts by weight of sodium chloride solution that concentration is 8%, takes upper layer oil liquid after stratification, and
Water and 20 parts by weight of sodium hydroxide are added in oil liquid, oil liquid terminal pH is 6.5-7.5.
C) oil liquid after neutralizing, ethyl orthosilicate, methyltriethoxysilane and the ethyl alcohol of formula ratio, in 55 DEG C of item are taken
It is stirred evenly under part and obtains siliceous tanning agent.
Embodiment 4
A kind of preparation method of siliceous tanning agent is present embodiments provided, according to parts by weight includes the following raw material: positive silicic acid
18 parts of ethyl ester, 30 parts of methyltriethoxysilane, 120 parts of sulfonated castor oil, 4 parts of water and 1 part of ethyl alcohol.
The preparation method of above-mentioned siliceous tanning agent carries out in accordance with the following steps:
A) 105 parts by weight castor oil are added in reaction kettle, 15 parts sulfuric acids, reaction temperature is slowly added dropwise while stirring
25 DEG C, sulfuric acid will add in 3 hours.Reaction observes oil liquid color after carrying out at least 2 hours, and sulfonation is indicated if dark green
Reaction terminates.
B) oil liquid first is washed using 18 parts by weight of sodium chloride solution that concentration is 6%, takes upper layer oil liquid after stratification, and
Water and 30 parts by weight of sodium hydroxide are added in oil liquid, oil liquid terminal pH is 7-8.
C) oil liquid after neutralizing, ethyl orthosilicate, methyltriethoxysilane and the ethyl alcohol of formula ratio, in 65 DEG C of item are taken
It is stirred evenly under part and obtains siliceous tanning agent.
Embodiment 5
A kind of preparation method of siliceous tanning agent is present embodiments provided, according to parts by weight includes the following raw material: positive silicic acid
30 parts of ethyl ester, 18 parts of methyltriethoxysilane, 145 parts of sulfonated castor oil, 1 part of water and 4 parts of ethyl alcohol.
The preparation method of above-mentioned siliceous tanning agent carries out in accordance with the following steps:
A) 115 parts by weight castor oil are added in reaction kettle, 30 parts sulfuric acids, reaction temperature is slowly added dropwise while stirring
35 DEG C, sulfuric acid will add in 3 hours.Reaction observes oil liquid color after carrying out at least 2 hours, and sulfonation is indicated if dark green
Reaction terminates.
B) oil liquid first is washed using 20 parts by weight of sodium chloride solution that concentration is 5%, takes upper layer oil liquid after stratification, and
Water and 15 parts by weight of sodium hydroxide are added in oil liquid, oil liquid terminal pH is 6-7.
C) oil liquid after neutralizing, ethyl orthosilicate, methyltriethoxysilane and the ethyl alcohol of formula ratio, in 70 DEG C of item are taken
It is stirred evenly under part and obtains siliceous tanning agent.
Embodiment 6
A kind of preparation method of siliceous tanning agent is present embodiments provided, according to parts by weight includes the following raw material: positive silicic acid
15 parts of ethyl ester, 35 parts of methyltriethoxysilane, 110 parts of sulfonated castor oil, 5 parts of water and 1 part of ethyl alcohol.
The preparation method of above-mentioned siliceous tanning agent carries out in accordance with the following steps:
A) 100 parts by weight castor oil are added in reaction kettle, 10 parts sulfuric acids, reaction temperature is slowly added dropwise while stirring
35 DEG C, sulfuric acid will add in 3 hours.Reaction observes oil liquid color after carrying out at least 2 hours, and sulfonation is indicated if dark green
Reaction terminates.
B) oil liquid first is washed using 5 parts by weight of sodium chloride solution that concentration is 15%, takes upper layer oil liquid after stratification, and
Water and 15 parts by weight of sodium hydroxide are added in oil liquid, oil liquid terminal pH is 6-7.
C) oil liquid after neutralizing, ethyl orthosilicate, methyltriethoxysilane and the ethyl alcohol of formula ratio, in 50 DEG C of item are taken
It is stirred evenly under part and obtains siliceous tanning agent.
Embodiment 7
A kind of preparation method of siliceous tanning agent is present embodiments provided, according to parts by weight includes the following raw material: positive silicic acid
35 parts of ethyl ester, 15 parts of methyltriethoxysilane, 155 parts of sulfonated castor oil, 1 part of water and 5 parts of ethyl alcohol；Wherein sulfonated castor oil is
Commercial product, pH 6.0-9.0；Above-mentioned raw materials are uniformly mixed according to formula ratio and obtain siliceous tanning agent.
Embodiment 8
A kind of preparation method of siliceous tanning agent is present embodiments provided, the difference from embodiment 1 is that, esters of silicon acis is positive silicon
Propyl propionate, silane coupling agent are dimethyl diethoxysilane.
Embodiment 9
This comparative example provides a kind of preparation method of siliceous tanning agent, the difference from embodiment 1 is that, siliceous tanning agent is by weight
Measuring number meter includes the following raw material: 10 parts of ethyl orthosilicate, 40 parts of methyltriethoxysilane, 80 parts of sulfonated castor oil, water 10
Part；Sulfonated castor oil is reacted to obtain by 65 parts by weight castor oil and 15 parts sulfuric acids.
Embodiment 10
This comparative example provides a kind of preparation method of siliceous tanning agent, the difference from embodiment 1 is that, siliceous tanning agent is by weight
Measuring number meter includes the following raw material: 40 parts of ethyl orthosilicate, 10 parts of methyltriethoxysilane, 170 parts of sulfonated castor oil, water 60
Part and 10 parts of ethyl alcohol；Sulfonated castor oil is reacted to obtain by 150 parts by weight castor oil and 30 parts sulfuric acids.
Embodiment 11
A kind of preparation method of siliceous tanning agent is present embodiments provided, the difference from embodiment 1 is that bleeding agent is alkyl
Sodium sulfovinate.
Embodiment 12
A kind of preparation method of siliceous tanning agent is present embodiments provided, the difference from embodiment 1 is that bleeding agent is alkyl
Phenol polyethenoxy ether.
Comparative example 1
This comparative example provides a kind of preparation method of siliceous tanning agent, the difference from embodiment 1 is that without silane coupled
Agent.
Comparative example 2
This comparative example provides a kind of preparation method of siliceous tanning agent, the difference from embodiment 1 is that being free of esters of silicon acis.
Comparative example 3
This comparative example provides a kind of preparation method of siliceous tanning agent, the difference from embodiment 1 is that being free of sulfonation castor-oil plant
Oil.
Effect example
The siliceous tanning agent that embodiment 1-12 and comparative example 1-3 are prepared is carried out on scytoblastema with chrome tanning agent in the market
Tanning, effective additional amount account for experiment and are calculated with sour 1.5-2.0 times of skin weight gain, additional amount 5-15wt%, comparing result such as following table institute
Show:
From above table as can be seen that siliceous tanning agent provided by the invention preparation method, using esters of silicon acis as silicon source before
Body is driven, using silane coupling agent as organic modifiers, can finally generate the improved silica containing more active group.The dioxy
SiClx can be effectively improved the shrinkage temperature, tensile strength, tearing strength of finished leather with the collagen strong effect on fiber.
The tanned leather of siliceous tanning agent provided in this embodiment is white, the tanning suitable for Bai Pi and light skin.By embodiment
The proportion as can be seen that formula ratio by adjusting each raw material is compared with comparative example, can optimize the tanning performance of siliceous tanning agent,
The siliceous tanning agent tanning performance that wherein embodiment 1 is prepared is best.Pass through it can be seen from comparative example 1 and the comparison of embodiment 1
It can make silica surface that there are more active groups using silane coupling agent modification silica, make silica and fibre
Collagen effect in dimension is strong.Sulfonated castor oil can promote siliceous it can be seen from comparative example 3 and the comparison of embodiment 1
The infiltration of tanning agent keeps leather tanning more abundant.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of preparation method of siliceous tanning agent, which is characterized in that by esters of silicon acis, silane coupling agent, bleeding agent, water and cosolvent
The siliceous tanning agent is obtained after mixing.
2. preparation method according to claim 1, which is characterized in that first mix water and bleeding agent, then by system
PH is adjusted to neutrality, and esters of silicon acis, silane coupling agent and cosolvent is then added, and maintaining mixed system temperature is 50-70 DEG C,
The siliceous tanning agent is obtained after mixing evenly.
3. preparation method according to claim 2, which is characterized in that carry out pH adjusting by the way that pH adjusting agent is added；
Wherein, the pH adjusting agent includes potassium hydroxide, sodium hydroxide or ammonium hydroxide, preferably sodium hydroxide；
Preferably, pH to 6.5-7.5 is adjusted.
4. preparation method according to claim 1, which is characterized in that the silane coupling agent is Y (CH2)nSiX3；
Wherein, Y is hydrogen, vinyl, epoxy group, amino, methacryloxy or urea groups；X is halogen, methoxyl group, ethyoxyl
Or acetoxyl group；The integer of n=0-3；
Preferably, Y is hydrogen, vinyl or epoxy group；X is methoxy or ethoxy；The integer of n=0-3；
It is highly preferred that the silane coupling agent is methyltriethoxysilane.
5. preparation method according to claim 1, which is characterized in that the esters of silicon acis includes methyl orthosilicate, positive silicic acid
Ethyl ester, positive silicic acid propyl ester；Preferably ethyl orthosilicate.
6. preparation method according to claim 1, which is characterized in that the cosolvent is C1-C8 low-carbon alcohols；
Preferably, the C1-C8 low-carbon alcohols include methanol, ethyl alcohol, propyl alcohol or amylalcohol, more preferably ethyl alcohol.
7. preparation method according to claim 1, which is characterized in that the bleeding agent is mainly anti-with sulfonating agent by castor oil
It should obtain sulfonated castor oil；
Preferably, it reacts 100-120 parts of castor oil and 10-35 parts of sulfonating agent to obtain sulfonated castor oil；
Preferably, sulfonating agent is sulfuric acid；
Preferably, the sulfonated castor oil is made by the following method: sulphur being added dropwise into castor oil under conditions of 25-35 DEG C
Acid, the time that sulfuric acid is added dropwise are no more than 3 hours；And reacting when the oil liquid of castor oil is dark green terminates, then using dense
The sodium chloride solution 5-20 parts by weight that degree is 5%-15% wash oil liquid.
8. preparation method described in any one of -7 according to claim 1, which is characterized in that number in parts by weight, is used
It is as follows with the raw material for preparing siliceous tanning agent: 15-35 parts of esters of silicon acis, 15-35 parts of silane coupling agent, 110-155 parts of bleeding agent, water 1-
5 parts and cosolvent 1-5 parts；
Preferably, in parts by weight, the raw material to prepare siliceous tanning agent is as follows for number: 18-30 parts of esters of silicon acis, silane are even
Agent 18-30 parts of connection, 120-145 parts of bleeding agent, 1-4 parts of water and 1-4 parts of cosolvent；
It is highly preferred that number is in parts by weight, the raw material to prepare siliceous tanning agent is as follows: 20-25 parts of esters of silicon acis, silane
20-25 parts of coupling agent, 128-137 parts of bleeding agent, 2-3 parts of water and 2-3 parts of cosolvent；
Preferably, the raw material to prepare siliceous tanning agent further includes 5-35 parts of pH adjusting agent, and preferably 10-30 parts, more preferably
20-25 parts.
9. a kind of siliceous tanning agent that preparation method of any of claims 1-8 is prepared.
10. application of the siliceous tanning agent as claimed in claim 9 in leather arrangement.
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| CN113061670A (en) * | 2021-03-31 | 2021-07-02 | 四川大学 | Method for modifying superhydrophobicity of substance containing collagen fibers, method for tanning without tanning agent, and leather product |
| CN115433788A (en) * | 2022-08-09 | 2022-12-06 | 四川达威科技股份有限公司 | Silicon-containing composite tanning agent, preparation method and application thereof |
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| CN115433788A (en) * | 2022-08-09 | 2022-12-06 | 四川达威科技股份有限公司 | Silicon-containing composite tanning agent, preparation method and application thereof |
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