A kind of sulfonation class leather fatting agent of fatty acids low-carbon ester and preparation method thereof
Technical field
The present invention relates to a kind of leather fat and preparation method thereof, more particularly, to a kind of sulfonation of fatty acids low-carbon ester
Class leather fatting agent and preparation method thereof.
Background technology
Stuffing operation during leather produces is to process leather with grease or fatting agent under certain process conditions, makes leather
Absorb a certain amount of grease and give the process of leather certain physics, mechanical performance and serviceability.Stuffing can be by chemistry
So that the grease that each fiber within leather is had lubrication is wrapped up or fiber surface is affine a large amount of
" oiliness " molecule, balance leather fiber surface energy, make original high energy surface be changed into low-energy surface, increase interfibrous phase
Mutually mobility, thus preventing that leather is hardened, jackknifing, makes leather have corresponding elasticity, toughness, extensibility and flexibility etc. again
Good physical and mechanical property, so stuffing is possible to change leather final mechanical performance, aesthetic property and feel.At present, state
In interior leather fat product, sulfonation class leather fatting agent is mainly with unsaturated fatty acid ester, such as soap stock acidification oil etc., direct gas
Prepared by phase sulfonation, after processing, product mobility is preferable.But, due in carbochain, there is carbon-carbon double bond, in sulfonating reaction, mainly
It is carbon-carbon double bond and SO3Reaction, and ester group and SO3Percentage bound not high.And the grease containing carbon-carbon double bond is old through sulfonation
After change, product color is deep, easy coking charing, so having the grease of double bond typically without aging, directly neutralizes, institute after sulfonation
The product sulphonation rate obtaining is relatively low, and product stability is poor.It is subject to material quality differentia influence particularly in process of producing product, cause
Make product quality situation unstable, lamination easily in product, using often there being the phenomenons such as oil slick to occur, cause product not
Qualification rate increases, and also increases the cost in production.In addition, the appearance luster of traditional sulfonation class leather fatting agent is generally reddish brown
Color liquid, reaches downstream application reluctantly and the color and luster of product is required.In addition, fatting agent is typically related to the iodine value of raw material, typically
In the case of, raw material iodine value is higher, identical sulphonation rate, and raw material color and luster can become deeper, therefore for reaching color and luster requirement, the sulphur of raw material
Rate nor too high, raw material availability is low.
In order to improve ester group and the SO of fatty acid ester3Percentage bound, there have been attempts using through catalytic hydrogenation saturation
Fatty acid ester prepares fatting agent as raw material, but because the freezing point of polyunsaturated fatty acid ester is high, product freezing point after sulfonation
Increase, be the lotion of curdled appearance or solid under normal temperature, or more precipitation, its dissolution time is long, uses very
Inconvenience, commercially also has no competitiveness.Thus, for the use at visitor family under the influence of not, polyunsaturated fatty acid ester always with
Carry out the primary raw material all not as leather fat.
Content of the invention
An object of the present invention is to provide a kind of sulfonation class leather fatting agent of fatty acids low-carbon ester, and this leather adds
Fat agent with saturated fatty acid low-carbon ester for raw material is sulfonated and burin-in process after obtain, be fluid product, not only facilitate lower visitor
The use at family, and stable in properties, have excellent fillibility, leather hand feeling can be made plentiful, soft, leather surface is smooth.
The purpose of the present invention is achieved through the following technical solutions:A kind of sulfonation class leather of fatty acids low-carbon ester
Fatting agent, it is prepared from by following methods:
(1) sulfonation:With saturated fatty acid low-carbon ester as raw material, sulfonated acquisition alpha-sulfonated fatty acid low-carbon ester;
(2) aging:Add grease or modified grease toward in described alpha-sulfonated fatty acid low-carbon ester, be placed in old after mixing
Change and in cylinder, carry out aging reaction, obtain aging alpha-sulfonated fatty acid low-carbon ester;
(3) decolour:Desolventing technology is carried out to described aging rear alpha-sulfonated fatty acid low-carbon ester;
(4) adjust pH value:The pH of the alpha-sulfonated fatty acid low-carbon ester after decolouring is adjusted to by 4-8 using nertralizer, obtains skin
Leather fatting agent.
Carbochain in saturated fatty acid low-carbon ester participates in sulfonating reaction due to substantially not having carbon-carbon double bond, it is to avoid saturated fat
Fat acid low-carbon ester and SO3Generate the deeper material of color and luster in complete sulfonation, so after sulfonation with aging technique, SO3In ester
React completely on a position of base group, improve the extent of reaction, and more than 90% reactivity can be reached.In aging technique,
One side grease dilutes alpha-sulfonated fatty acid low-carbon ester, simultaneously as product stuffing composition, also improves product flow regime, makes
It is in liquid for obtaining final products, and on the other hand, in ageing process, grease or modified grease absorb further through alpha-sulfonated fatty
The unnecessary SO of sour low-carbon ester3, make product more stable, and be conducive to forming stable emulsion with grease, in currier
Excellent stuffing effect is reached in skill.The lighter of alpha-sulfonated fatty acid low-carbon ester after desolventing technology, more meets lower visitor
The use requirement at family, adjusts pH 4 to 8, can improve product stability, makes fatting agent be less likely to occur in storage to decompose.
In described step (1), the temperature of described sulfonating reaction is 50-70 DEG C, and the chuck water temperature of sulfonation reactor is 50-80
DEG C, SO3SO in dilution wind3Volume fraction is 5-7%, makes saturation low-carbon ester of fatty acid and SO in sulfonation3Between mol ratio exist
Between 0.90-1.20.
Described saturated fatty acid low-carbon ester chemical formula is R1CH2COOR2, wherein R1It is the saturation alkane that carbochain is 12 to 20
Base, R2It is the saturated alkyl that carbochain is 1 to 4.Adopt saturated fatty acid low-carbon ester below 0.5 for the iodine value in the present invention, can
To be one of above-mentioned saturated fatty acid low-carbon ester or two or more mixtures.
In described step (2), described ageing time is 20-40 minute, aging tank chuck water temperature 70-90 DEG C.
In described step (2), the mass ratio between described alpha-sulfonated fatty acid low-carbon ester and grease is 15-25:100.Described
Grease or modified grease, they are neutrality or acidity, original or the plant through recycling or animal fat.
In described step (3), desolventing technology is carried out to the alpha-sulfonated fatty acid low-carbon ester after aging using decolorising agent, its consumption
For the 1-5% of alpha-sulfonated fatty acid low-carbon ester gross mass, bleaching temperature is 70-90 DEG C, bleaching time 20-40 minute.As the present invention
An embodiment, described decolorising agent be hydrogen peroxide.
In described step (4), nertralizer is ammoniacal liquor or NaOH or potassium hydroxide.
The second object of the present invention is to provide the system of the above-mentioned sulfonation class leather fatting agent containing saturated fatty acid low-carbon ester
Preparation Method.
Second goal of the invention of the present invention is achieved through the following technical solutions:A kind of sulphur containing saturated fatty acid low-carbon ester
Change the preparation method of class leather fatting agent, comprise the following steps:
(1) sulfonation:With saturated fatty acid low-carbon ester as raw material, sulfonated acquisition alpha-sulfonated fatty acid low-carbon ester;
(2) aging:Add grease or modified grease toward in described alpha-sulfonated fatty acid low-carbon ester, be placed in old after mixing
Change and in cylinder, carry out aging reaction, obtain aging alpha-sulfonated fatty acid low-carbon ester;
(3) decolour:Desolventing technology is carried out to described aging rear alpha-sulfonated fatty acid low-carbon ester;
(4) adjust pH value:The pH of the alpha-sulfonated fatty acid low-carbon ester after decolouring is adjusted to by 4-8 using nertralizer, obtains skin
Leather fatting agent.
In described step (1), the temperature of described sulfonating reaction is 50-70 DEG C, and the chuck water temperature of sulfonation reactor is 50-80
DEG C, SO3SO in dilution wind3Volume fraction is 5-7%, makes saturation low-carbon ester of fatty acid and SO in sulfonation3Between mol ratio exist
Between 0.90-1.20.
Described saturated fatty acid low-carbon ester chemical formula is R1CH2COOR2, wherein R1It is the saturation alkane that carbochain is 12 to 20
Base, R2It is the saturated alkyl that carbochain is 1 to 4.Adopt iodine value in the present invention 0
.5 following saturated fatty acid low-carbon ester, can be one of above-mentioned saturated fatty acid low-carbon ester or two or more
Mixture.
In described step (2), described ageing time is 20-40 minute, aging tank chuck water temperature 70-90 DEG C.
In described step (2), the mass ratio between described alpha-sulfonated fatty acid low-carbon ester and grease is 15-25:100.Described
Grease or modified grease, they are neutrality or acidity, original or the plant through recycling or animal fat, such as kitchen
Oil recovery, castor oil, chlorination lard, palm oil etc..
In described step (3), desolventing technology is carried out to the alpha-sulfonated fatty acid low-carbon ester after aging using decolorising agent, its consumption
For the 1-5% of alpha-sulfonated fatty acid low-carbon ester gross mass, bleaching temperature is 70-90 DEG C, bleaching time 20-40 minute.As the present invention
An embodiment, described decolorising agent be hydrogen peroxide.
In described step (4), nertralizer is ammoniacal liquor or NaOH or potassium hydroxide.
The present invention compared with prior art has advantages below:
(1) leather fat that the present invention provides is raw material through sulfonation, aging, decolouring by saturated fatty acid low-carbon ester
It is prepared with after neutralisation treatment, be fluid product, the use of suitable downstream client, product is stable, in configuration 1:9 aqueous solution 24
Hour not oil slick, is applied to leather greasing, has excellent fillibility, can make that leather hand feeling is plentiful, and leather surface is smooth.
(2) present invention carries out sulfonation, base in the carbochain of saturated fatty acid low-carbon ester with saturated fatty acid low-carbon ester for raw material
There is no carbon-carbon double bond on this, in sulfonating reaction, SO3Only can be reacted with ester group, be improved SO3Percentage bound with ester group.And
Aging middle grease and alpha-sulfonated fatty acid low-carbon ester are not simple mixing, and reaction complicated further occurs in insulating process,
The double bond improving anion or acid esters further with grease continues reaction, improves sulphonation rate, advantageously adds in raising leather
The stability of fat agent, is allowed to be not easy to be layered, is conducive to client to use.
(3) present invention selects iodine value to be less than the saturated fatty acid low-carbon ester of 0.5 technical grade, advantageously reduces follow-up
Aging technique in there is the side reaction that color and luster deepens, and so that sulfonation main reaction in ageing process is improved.
(4) present invention, through burin-in process, makes the anion in leather fat improve further, so that reactivity is reached
More than 90%.
(5) in the present invention, grease dilutes alpha-sulfonated fatty acid low-carbon ester, improves product flow regime, makes final gained
Product be in a liquid state;On the other hand, in ageing process, grease or modified grease absorb further by low through alpha-sulfonated fatty acid
The SO discharging in aging reaction in carbon ester3, and be conducive to forming stable emulsion with grease, make product in currier
Excellent stuffing effect is reached in skill.
Specific embodiment
Saturated fatty acid low-carbon ester chemical formula in following examples of the present invention is R1CH2COOR2, wherein R1It is that carbochain is
12 to 20 saturated alkyl, R2It is the saturated alkyl that carbochain is 1 to 4.Adopt saturated fat below 0.5 for the iodine value in the present invention
Fat acid low-carbon ester.And can be one of above-mentioned saturated fatty acid low-carbon ester or two or more mix in any proportion mixed
Compound.As one embodiment of the present invention, the sulfonation of saturated fatty acid low-carbon ester adopts gas phase SO3Falling film sulfonation method is entered
OK.
Embodiment 1:
It is the saturated fatty acid methyl ester of C12 that the present embodiment adopts R1 carbochain, R1 carbochain is C14 saturated fatty acid methyl ester,
The mixture of the saturated fatty acid methyl ester for C18 for the saturated fatty acid methyl ester and R1 carbochain for C16 for the R1 carbochain is raw material, wherein,
R1 carbochain is that the saturated fatty acid methyl ester of C12 accounts for 35%;R1 carbochain is that the saturated fatty acid methyl ester of C14 accounts for 15%;R1 carbochain is C16
Saturated fatty acid methyl ester account for 33%;R1 carbochain is that the saturated fatty acid methyl ester of C18 accounts for 17%.
(1) sulfonation:Using gas phase falling film sulfonation/sulphation laboratory equipment, saturated fatty acid methyl ester is from design temperature
Raw material cold wall tank for 55 DEG C, through delivery pump, is transported to single tube reactor top by quantitative 250 gram/minute, full of feed space
After overflow to reactor wall, raw material pump using Frequency Converter Control saturated fatty acid methyl ester flow is, outside sulfonation reactor
Chuck water temperature is 70 DEG C.Liquid SO2Through gasification, control in 70 gram/minute through gas mass flow gauge, enter converter and turn
Turn to SO3(Conversion ratio commonly reaches 98%), and pass through Dilution air SO3, make SO3Volume-fraction concentration in gas is 6%,
Make saturated fatty acid methyl ester and SO in sulfonation3Between mol ratio be 1.15(±0.02).SO3Contact with saturated fatty acid methyl ester
Reactive absorption, acid product flows out from the bottom of gas-liquid separator, after question response system stability, obtains alpha-sulfonated fatty acid methyl esters
500g is in 5L beaker.
(2) aging:2000g kitchen oil recovery is taken to be placed in aging tank, old after mixing with alpha-sulfonated fatty acid methyl esters
Change and be incubated under the conditions of cylinder chuck water temperature is 85 DEG C and stir 30 minutes, carry out aging reaction, obtain aging alpha-sulfonated fatty acid first
Ester.
(3) decolour:Adding 20g hydrogen peroxide through aging alpha-sulfonated fatty acid methyl esters, and mixing continues to stir at 85 DEG C
Mix, decolour 30 minutes.
(4) adjust pH value:The temperature of the alpha-sulfonated fatty acid methyl esters after decolouring is reduced to about 40-45 DEG C, adds nertralizer
It is 6.5 that alpha-sulfonated fatty acid methyl esters is neutralized to pH by 15% ammoniacal liquor, and in N-process, temperature control is not surpassing 50 DEG C, finally gives red
The alpha-sulfonated fatty acid methyl esters of brown liquid shape.Configuration 1:9 aqueous solution 24 hours not oil slick.When being applied to leather greasing, have excellent
Good fillibility, can make that leather hand feeling is plentiful, and leather surface is smooth.
Embodiment 2:
It is the saturated fatty acid methyl ester of C18 that the present embodiment adopts the saturated fat acid butyl ester that R1 carbochain is C16 and R1 carbochain
Mixture be raw material, wherein, R1 carbochain be C16 saturated fat acid butyl ester account for 65%;R1 carbochain is the saturated fatty acid of C18
Butyl ester accounts for 35%.
(1) sulfonation:Using gas phase falling film sulfonation/sulphation laboratory equipment, saturated fat acid butyl ester is from design temperature
Raw material cold wall tank for 55 DEG C, through delivery pump, is transported to single tube reactor top by quantitative 324 gram/minute, full of feed space
After overflow to reactor wall, raw material pump using Frequency Converter Control saturated fat acid butyl ester flow is, outside sulfonation reactor
Chuck water temperature is 70 DEG C.Liquid SO2Through gasification, control in 65 gram/minute through gas mass flow gauge, enter converter and turn
Turn to SO3(Conversion ratio commonly reaches 98%), and pass through Dilution air SO3, make SO3Volume-fraction concentration in gas is 6%,
Make saturation fatty acid butyl ester and SO in sulfonation3Between mol ratio be 1.00(±0.02).SO3Contact with saturated fat acid butyl ester
Reactive absorption, acid product flows out from the bottom of gas-liquid separator, after question response system stability, obtains alpha-sulfonated fatty acid butyl ester
500g is in 5L beaker.
(2) aging:2500g castor oil is taken to be placed in aging tank, in aging tank after mixing with alpha-sulfonated fatty acid butyl ester
Chuck water temperature is incubated under the conditions of being 85 DEG C and stirs 30 minutes, carries out aging reaction, obtains aging alpha-sulfonated fatty acid butyl ester.
(3) decolour:Adding 20g hydrogen peroxide through aging alpha-sulfonated fatty acid butyl ester, and mixing continues to stir at 85 DEG C
Mix, decolour 30 minutes.
(4) adjust pH value:The temperature of the alpha-sulfonated fatty acid butyl ester after decolouring is reduced to about 40-45 DEG C, adds nertralizer
It is 7.5 that alpha-sulfonated fatty acid butyl ester is neutralized to pH by 16% sodium hydrate aqueous solution, in N-process temperature control not surpassing 50 DEG C,
Finally give the liquid alpha-sulfonated fatty acid butyl ester of rufous.Configuration 1:9 aqueous solution 24 hours not oil slick.It is applied to leather greasing
When, there is excellent fillibility, can make that leather hand feeling is plentiful, leather surface is smooth.
Embodiment 3:
The saturated fatty acid that the present embodiment adopts the saturated fat isopropyl propionate that R1 carbochain is C16 and R1 carbochain is C18 is different
The mixture of propyl ester is raw material, and wherein, R1 carbochain is that the saturated fat isopropyl propionate of C16 accounts for 65%;R1 carbochain is the saturation of C18
Isopropyl fatty acid ester accounts for 35%.
(1) sulfonation:Using gas phase falling film sulfonation/sulphation laboratory equipment, saturated fat isopropyl propionate is warm from setting
Spend the raw material cold wall tank for 70 DEG C, through delivery pump, be transported to single tube reactor top by quantitative 370 gram/minute, full of charging
Reactor wall is overflowed to, raw material pump using Frequency Converter Control saturated fat isopropyl propionate flow is, outside sulfonation reactor behind room
The chuck water temperature in portion is 80 DEG C.Liquid SO2Through gasification, control in 65 gram/minute through gas mass flow gauge, enter conversion
Tower is converted into SO3(Conversion ratio commonly reaches 98%), and pass through Dilution air SO3, make SO3Volume-fraction concentration in gas is
5%, make saturation isopropyl fatty acid ester and SO in sulfonation3Between mol ratio be 1.20(±0.02).SO3With saturated fatty acid isopropyl
Ester haptoreaction absorbs, and acid product flows out from the bottom of gas-liquid separator, after question response system stability, obtains alpha-sulfonated fatty
Isopropyl propionate 300g is in 5L beaker.
(2) aging:2000g chlorination lard is taken to be placed in aging tank, old after mixing with alpha-sulfonated fatty isopropyl propionate
Change and be incubated under the conditions of cylinder chuck water temperature is 90 DEG C and stir 20 minutes, carry out aging reaction, obtain aging alpha-sulfonated fatty acid different
Propyl ester.
(3) decolour:Adding 5g hydrogen peroxide through aging alpha-sulfonated fatty isopropyl propionate, and mixing continues to stir at 90 DEG C
Mix, decolour 20 minutes.
(4) adjust pH value:The temperature of the alpha-sulfonated fatty isopropyl propionate after decolouring is reduced to about 40-45 DEG C, adds neutralization
It is 8.0 that alpha-sulfonated fatty isopropyl propionate is neutralized to pH by agent 16% potassium hydroxide aqueous solution, and in N-process, temperature control is not surpassing 50
DEG C, finally give the liquid alpha-sulfonated fatty isopropyl propionate of rufous.Configuration 1:9 aqueous solution 24 hours not oil slick.It is applied to skin
During leather stuffing, there is excellent fillibility, can make that leather hand feeling is plentiful, leather surface is smooth.
Embodiment 4:
It is raw material that the present embodiment adopts the saturated fat acetoacetic ester that R1 carbochain is C18.
(1) sulfonation:Using gas phase falling film sulfonation/sulphation laboratory equipment, saturated fat acetoacetic ester is warm from setting
Spend the raw material cold wall tank for 50 DEG C, through delivery pump, be transported to single tube reactor top by quantitative 254 gram/minute, full of charging
Reactor wall is overflowed to, raw material pump using Frequency Converter Control saturated fat acetoacetic ester flow is, outside sulfonation reactor behind room
Chuck water temperature be 60 DEG C.Liquid SO2Through gasification, control in 65 gram/minute through gas mass flow gauge, enter converter
It is converted into SO3(Conversion ratio commonly reaches 98%), and pass through Dilution air SO3, make SO3Volume-fraction concentration in gas is
7%, make saturation fatty-acid ethyl ester and SO in sulfonation3Between mol ratio be 0.90(±0.02).SO3Connect with saturated fat acetoacetic ester
Tactile reactive absorption, acid product flows out from the bottom of gas-liquid separator, after question response system stability, obtains alpha-sulfonated fatty acid second
Ester 500g is in 5L beaker.
(2) aging:2000g palm oil is taken to be placed in aging tank, in aging tank after mixing with alpha-sulfonated fatty acetoacetic ester
Chuck water temperature is incubated under the conditions of being 70 DEG C and stirs 40 minutes, carries out aging reaction, obtains aging alpha-sulfonated fatty acetoacetic ester.
(3) decolour:Adding 25g hydrogen peroxide through aging alpha-sulfonated fatty acetoacetic ester, and mixing continues to stir at 70 DEG C
Mix, decolour 40 minutes.
(4) adjust pH value:The temperature of the alpha-sulfonated fatty acetoacetic ester after decolouring is reduced to about 40-45 DEG C, adds nertralizer
It is 6.0 that alpha-sulfonated fatty acetoacetic ester is neutralized to pH by 16% sodium hydrate aqueous solution, in N-process temperature control not surpassing 50 DEG C,
Finally give the liquid alpha-sulfonated fatty acetoacetic ester of rufous.Configuration 1:9 aqueous solution 24 hours not oil slick.It is applied to leather greasing
When, there is excellent fillibility, can make that leather hand feeling is plentiful, leather surface is smooth.
Comparative example 1
It is the saturated fatty acid methyl ester of C12 that the present embodiment adopts R1 carbochain, R1 carbochain is C14 saturated fatty acid methyl ester,
The mixture of the saturated fatty acid methyl ester for C18 for the saturated fatty acid methyl ester and R1 carbochain for C16 for the R1 carbochain is raw material, wherein,
R1 carbochain is that the saturated fatty acid methyl ester of C12 accounts for 35%;R1 carbochain is that the saturated fatty acid methyl ester of C14 accounts for 15%;R1 carbochain is C16
Saturated fatty acid methyl ester account for 33%;R1 carbochain is that the saturated fatty acid methyl ester of C18 accounts for 17%.
(1) sulfonation:Using gas phase falling film sulfonation/sulphation laboratory equipment, saturated fatty acid methyl ester is from design temperature
Raw material cold wall tank for 55 DEG C, through delivery pump, is transported to single tube reactor top by quantitative 250 gram/minute, full of feed space
After overflow to reactor wall, raw material pump using Frequency Converter Control saturated fatty acid methyl ester flow is, outside sulfonation reactor
Chuck water temperature is 70 DEG C.Liquid SO2Through gasification, control in 65 gram/minute through gas mass flow gauge, enter converter and turn
Turn to SO3(Conversion ratio commonly reaches 98%), and pass through Dilution air SO3, it is 6% that gas makes its volume fraction, makes saturation in sulfonation
Fatty acid methyl ester and SO3Between mol ratio be 1.15(±0.02).SO3Absorb with saturated fatty acid methyl ester haptoreaction, acid
Product flows out from the bottom of gas-liquid separator, after question response system stability, obtains alpha-sulfonated fatty acid methyl esters 500g in 5L beaker
In.
(2) 2000g kitchen oil recovery is taken to mix with alpha-sulfonated fatty acid methyl esters.
(3) decolour:Add 20g hydrogen peroxide in kitchen oil recovery with alpha-sulfonated fatty acid mixtures of methyl esters, and at 85 DEG C
Mixing continues stirring, decolours 30 minutes.
(4) adjust pH value:The temperature of the alpha-sulfonated fatty acid methyl esters after decolouring is reduced to about 40-45 DEG C, adds nertralizer
It is 7.5 that alpha-sulfonated fatty acid methyl esters is neutralized to pH by 16% sodium hydrate aqueous solution, in N-process temperature control not surpassing 50 DEG C,
Finally give the liquid alpha-sulfonated fatty acid methyl esters of rufous.Configuration 1:Oil slick in 9 aqueous solution 24 hours.
The present invention can be summarized without prejudice to the concrete form of the spirit or essential characteristics of the present invention with others.The present invention's
The embodiment above all can only be considered the description of the invention rather than restriction.Therefore every flesh and blood according to the present invention
Any trickle amendment, equivalent variations and the modification that above example is made, belongs in the range of technical solution of the present invention.