Sulfonation class leather fat of a kind 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, sulfonation class leather fat particularly relating to a kind of fatty acids low-carbon ester and preparation method thereof.
Background technology
Stuffing operation in leather production under certain processing condition, processes leather with grease or fatting agent, makes leather absorb a certain amount of grease and give the process of removing from office certain physics, mechanical property and use properties.Stuffing can make each fiber of leather inside be wrapped up or affine " oiliness " molecule in a large number of fiber surface by the grease with lubrication by chemistry and physical action, balance leather fiber surface energy, original high energy surface is made to change low-energy surface into, increase interfibrous mutual mobility, thus prevent leather from hardening, jackknifing, leather is made again to have the good physical and mechanical property such as corresponding elasticity, toughness, extensibility and flexibility, so stuffing likely changes leather final mechanical property, aesthetic property and feel.At present, in domestic leather fat product, sulfonation class leather fat is mainly with unsaturated fatty acid ester, and as soap stock acidifying wet goods, direct gas phase xanthation preparation, after processing, product mobility is better.But, owing to there is carbon-carbon double bond in carbochain, in sulfonation reaction, mainly carbon-carbon double bond and SO
3reaction, and ester group and SO
3combination rate not high.And the grease containing carbon-carbon double bond is after oversulfonate is aging, product color is dark, and easy coking charing, so have the grease of double bond generally without aging, directly neutralize after sulfonation, the product sulphonation rate of gained is relatively on the low side, and product stability is poor.Particularly be subject to raw materials quality differentia influence in process of producing product, causing quality product situation unstable, easily there is demixing phenomenon in product, uses phenomenons such as often having oil slick to occur, causes product disqualification rate to increase, too increase the cost in production.In addition, the appearance luster of traditional sulfonation class leather fat is generally reddish-brown liquid, reaches the color and luster requirement of downstream application to product reluctantly.In addition, fatting agent is general relevant to the iodine value of raw material, and generally, raw material iodine value is higher, identical sulphonation rate, and raw material color and luster can become darker, and therefore for reaching color and luster requirement, the sulphonation rate of raw material can not be too high, and raw material availability is low.
In order to improve ester group and the SO of fatty acid ester
3combination rate, once someone attempted adopting and prepared fatting agent through the polyunsaturated fatty acid ester of shortening as raw material, but because the zero pour of polyunsaturated fatty acid ester is high, after sulfonation, product zero pour also increases, be lotion or the solid of curdled appearance under normal temperature, or more precipitation, its dissolution time is long, use very inconvenient, commercially also have no competitive power.Thus, in order to not affect the use of downstream client, polyunsaturated fatty acid ester is not all the time as the main raw material of leather fat.
Summary of the invention
An object of the present invention is the sulfonation class leather fat providing a kind of fatty acids low-carbon ester, this leather fat with saturated fatty acid low-carbon ester for raw material obtains after sulfonation and burin-in process, for liquid product, not only facilitate the use of downstream client, and stable in properties, have excellent fillibility, leather hand feeling can be made plentiful, soft, and leather surface is smooth.
The object of the invention is to be achieved through the following technical solutions: a kind of sulfonation class leather fat of fatty acids low-carbon ester, it is prepared from by following methods:
(1) sulfonation: with saturated fatty acid low-carbon ester for raw material, obtains alpha-sulfonated fatty acid low-carbon ester through sulfonation;
(2) aging: in described alpha-sulfonated fatty acid low-carbon ester, to add grease or modified grease, mix to be placed in aging tank and 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: adopt neutralizing agent to be 4-8 by the pH regulator of the alpha-sulfonated fatty acid low-carbon ester after decolouring, obtain leather fat.
Carbochain in saturated fatty acid low-carbon ester participates in sulfonation reaction owing to substantially not having carbon-carbon double bond, avoids saturated fatty acid low-carbon ester and SO
3the darker material of color and luster is generated when complete sulfonation, so after oversulfonate and aging technique, SO
3the a position of ester group group reacts completely, improves level of response, and the reactivity of more than 90% can be reached.In aging technique, grease dilutes alpha-sulfonated fatty acid low-carbon ester on the one hand, simultaneously as product stuffing composition, also improve product flow state, the finished product are made to be liquid, on the other hand, in weathering process, grease or modified grease absorb further through the unnecessary SO of alpha-sulfonated fatty acid low-carbon ester
3, make product more stable, and be conducive to forming stable emulsion with grease, in leather greasing technique, reach excellent stuffing effect.The lighter of alpha-sulfonated fatty acid low-carbon ester after desolventing technology, more meets the service requirements of downstream client, regulates 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 sulfonation reaction is 50-70 DEG C, and the chuck water temperature of sulfonation reactor is 50-80 DEG C, SO
3sO in dilution wind
3volume fraction is 5-7%, makes saturated low-carbon ester of fatty acid and SO in sulfonation
3between mol ratio between 0.90-1.20.
Described saturated fatty acid low-carbon ester chemical formula is R
1cH
2cOOR
2, wherein R
1to be carbochain be 12 to 20 saturated alkyl, R
2to be carbochain be 1 to 4 saturated alkyl.Adopting the saturated fatty acid low-carbon ester of iodine value below 0.5 in the present invention, can be one or more the mixture in above-mentioned saturated fatty acid low-carbon ester.
In described step (2), described digestion 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 through the plant of recirculation or animal grease.
In described step (3), adopt discoloring agent to carry out desolventing technology to the alpha-sulfonated fatty acid low-carbon ester after aging, its consumption is the 1-5% of alpha-sulfonated fatty acid low-carbon ester total mass, and bleaching temperature is 70-90 DEG C, bleaching time 20-40 minute.As one embodiment of the present of invention, described discoloring agent is hydrogen peroxide.
In described step (4), neutralizing agent is ammoniacal liquor or sodium hydroxide or potassium hydroxide.
Two of object of the present invention is the preparation method providing the above-mentioned sulfonation class leather fat containing saturated fatty acid low-carbon ester.
The present invention's second goal of the invention is achieved through the following technical solutions: a kind of preparation method of the sulfonation class leather fat containing saturated fatty acid low-carbon ester, comprises the following steps:
(1) sulfonation: with saturated fatty acid low-carbon ester for raw material, obtains alpha-sulfonated fatty acid low-carbon ester through sulfonation;
(2) aging: in described alpha-sulfonated fatty acid low-carbon ester, to add grease or modified grease, mix to be placed in aging tank and 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: adopt neutralizing agent to be 4-8 by the pH regulator of the alpha-sulfonated fatty acid low-carbon ester after decolouring, obtain leather fat.
In described step (1), the temperature of described sulfonation reaction is 50-70 DEG C, and the chuck water temperature of sulfonation reactor is 50-80 DEG C, SO
3sO in dilution wind
3volume fraction is 5-7%, makes saturated low-carbon ester of fatty acid and SO in sulfonation
3between mol ratio between 0.90-1.20.
Described saturated fatty acid low-carbon ester chemical formula is R
1cH
2cOOR
2, wherein R
1to be carbochain be 12 to 20 saturated alkyl, R
2to be carbochain be 1 to 4 saturated alkyl.Adopt iodine value 0 in the present invention
.5 following saturated fatty acid low-carbon ester can be one or more the mixture in above-mentioned saturated fatty acid low-carbon ester.
In described step (2), described digestion 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 through the plant of recirculation or animal grease, as meal kitchen refiltered oil, Viscotrol C, chlorination lard, palm wet goods.
In described step (3), adopt discoloring agent to carry out desolventing technology to the alpha-sulfonated fatty acid low-carbon ester after aging, its consumption is the 1-5% of alpha-sulfonated fatty acid low-carbon ester total mass, and bleaching temperature is 70-90 DEG C, bleaching time 20-40 minute.As one embodiment of the present of invention, described discoloring agent is hydrogen peroxide.
In described step (4), neutralizing agent is ammoniacal liquor or sodium hydroxide or potassium hydroxide.
the present invention compared with prior art has the following advantages:
(1) by saturated fatty acid low-carbon ester, to be raw material prepare leather fat provided by the invention after oversulfonate, aging, decolouring and neutralizing treatment obtains, for liquid product, be applicable to the use of downstream client, product is stablized, at the configuration 1:9 aqueous solution 24 hours not oil slick, be applied to leather greasing, there is excellent fillibility, leather hand feeling can be made plentiful, and leather surface is smooth.
(2) the present invention is with saturated fatty acid low-carbon ester for raw material carries out sulfonation, there is no carbon-carbon double bond in the carbochain of saturated fatty acid low-carbon ester, in sulfonation reaction, and SO
3only can react with ester group, improve SO
3with the combination rate of ester group.And aging middle grease and alpha-sulfonated fatty acid low-carbon ester are not simple mixing, reaction complicated is further there is in insulating process, the double bond of further raising negatively charged ion or acid esters and grease continues to react, improve sulphonation rate, advantageously in the stability improving leather fat, make it to be not easy layering, be conducive to client and use.
(3) the present invention selects iodine value to be less than the saturated fatty acid low-carbon ester of the technical grade of 0.5, is conducive to reducing side reaction color and luster occurring in follow-up aging technique and deepens, and sulfonation main reaction in weathering process is improved.
(4) the present invention is through burin-in process, makes the negatively charged ion in leather fat improve further, makes reactivity reach more than 90%.
(5) in the present invention, grease dilutes alpha-sulfonated fatty acid low-carbon ester, improves product flow state, and the product of final gained is in a liquid state; On the other hand, in weathering process, grease or modified grease absorb further by the SO discharged in aging reaction in alpha-sulfonated fatty acid low-carbon ester
3, and be conducive to forming stable emulsion with grease, make the stuffing effect that product reaches excellent in leather greasing technique.
Embodiment
Saturated fatty acid low-carbon ester chemical formula in following examples of the present invention is R
1cH
2cOOR
2, wherein R
1to be carbochain be 12 to 20 saturated alkyl, R
2to be carbochain be 1 to 4 saturated alkyl.Adopt the saturated fatty acid low-carbon ester of iodine value below 0.5 in the present invention.And can be one or more mixtures mixed in any proportion in above-mentioned saturated fatty acid low-carbon ester.As one embodiment of the present invention, the sulfonation of saturated fatty acid low-carbon ester adopts gas phase SO
3falling film sulfonation method is carried out.
embodiment 1:
The saturated fatty acid methyl ester that the present embodiment adopts R1 carbochain is the saturated fatty acid methyl ester of C12, R1 carbochain is C14 saturated fatty acid methyl ester, R1 carbochain is C16 and R1 carbochain are the mixture of the saturated fatty acid methyl ester of C18 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 that the saturated fatty acid methyl ester of C16 accounts for 33%; R1 carbochain is that the saturated fatty acid methyl ester of C18 accounts for 17%.
(1) sulfonation: use gas phase falling film sulfonation/sulfation laboratory equipment, saturated fatty acid methyl ester is the raw material cold wall tank of 55 DEG C from design temperature, through transferpump, single tube reactor top is transported to by quantitative 250 gram/minute, reactor wall is overflowed to after being full of feed chamber, feedstock pump uses Frequency Converter Control saturated fatty acid methyl ester flow to be that the chuck water temperature of sulfonation reactor outside is 70 DEG C.Liquid SO
2through gasification, control, in 70 gram/minute, to enter converter and be converted into SO through mass-flow gas meter
3(transformation efficiency generally reaches 98%), and by Dilution air SO
3, make SO
3volume-fraction concentration in gas is 6%, makes saturated fatty acid methyl ester and SO in sulfonation
3between mol ratio be 1.15(± 0.02).SO
3absorb with saturated fatty acid methyl ester contact reacts, 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.
(2) aging: to get eat kitchen refiltered oil of 2000g and mix with alpha-sulfonated fatty acid methyl esters and be placed in aging tank, be incubated under aging tank chuck water temperature is 85 DEG C of conditions and stir 30 minutes, carrying out aging reaction, obtaining aging alpha-sulfonated fatty acid methyl esters.
(3) decolour: adding 20g hydrogen peroxide through aging alpha-sulfonated fatty acid methyl esters, and at 85 DEG C, mixing continues to stir, and decolours 30 minutes.
(4) adjust ph: the temperature of the alpha-sulfonated fatty acid methyl esters after decolouring is reduced to about 40-45 DEG C, it is 6.5 that alpha-sulfonated fatty acid methyl esters is neutralized to pH by interpolation neutralizing agent 15% ammoniacal liquor, in N-process, temperature controls do not surpassing 50 DEG C, finally obtains the alpha-sulfonated fatty acid methyl esters that reddish-brown is liquid.The configuration 1:9 aqueous solution 24 hours not oil slick.When being applied to leather greasing, have excellent fillibility, leather hand feeling can be made plentiful, and leather surface is smooth.
embodiment 2:
The present embodiment adopts R1 carbochain to be the saturated fatty acid butyl ester of C16 and R1 carbochain to be the mixture of the saturated fatty acid methyl ester of C18 to be raw material, and wherein, R1 carbochain is that the saturated fatty acid butyl ester of C16 accounts for 65%; R1 carbochain is that the saturated fatty acid butyl ester of C18 accounts for 35%.
(1) sulfonation: use gas phase falling film sulfonation/sulfation laboratory equipment, saturated fatty acid butyl ester is the raw material cold wall tank of 55 DEG C from design temperature, through transferpump, single tube reactor top is transported to by quantitative 324 gram/minute, reactor wall is overflowed to after being full of feed chamber, feedstock pump uses Frequency Converter Control saturated fatty acid butyl ester flow to be that the chuck water temperature of sulfonation reactor outside is 70 DEG C.Liquid SO
2through gasification, control, in 65 gram/minute, to enter converter and be converted into SO through mass-flow gas meter
3(transformation efficiency generally reaches 98%), and by Dilution air SO
3, make SO
3volume-fraction concentration in gas is 6%, makes saturated fatty acid butyl ester and SO in sulfonation
3between mol ratio be 1.00(± 0.02).SO
3absorb with saturated fatty acid butyl ester contact reacts, acid product flows out from the bottom of gas-liquid separator, after question response system stability, obtains alpha-sulfonated fatty acid butyl ester 500g in 5L beaker.
(2) aging: to get 2500g Viscotrol C and mix with alpha-sulfonated fatty acid butyl ester and be placed in aging tank, be incubated under aging tank chuck water temperature is 85 DEG C of conditions and stir 30 minutes, carrying out aging reaction, obtaining aging alpha-sulfonated fatty acid butyl ester.
(3) decolour: adding 20g hydrogen peroxide through aging alpha-sulfonated fatty acid butyl ester, and at 85 DEG C, mixing continues to stir, and decolours 30 minutes.
(4) adjust ph: the temperature of the alpha-sulfonated fatty acid butyl ester after decolouring is reduced to about 40-45 DEG C, it is 7.5 that alpha-sulfonated fatty acid butyl ester is neutralized to pH by interpolation neutralizing agent 16% aqueous sodium hydroxide solution, in N-process, temperature controls do not surpassing 50 DEG C, finally obtains the alpha-sulfonated fatty acid butyl ester that reddish-brown is liquid.The configuration 1:9 aqueous solution 24 hours not oil slick.When being applied to leather greasing, have excellent fillibility, leather hand feeling can be made plentiful, and leather surface is smooth.
embodiment 3:
The present embodiment adopts R1 carbochain to be the saturated fatty isopropyl propionate of C16 and R1 carbochain to be the mixture of the saturated fatty isopropyl propionate of C18 to be raw material, and wherein, R1 carbochain is that the saturated fatty isopropyl propionate of C16 accounts for 65%; R1 carbochain is that the saturated fatty isopropyl propionate of C18 accounts for 35%.
(1) sulfonation: use gas phase falling film sulfonation/sulfation laboratory equipment, saturated fatty isopropyl propionate is the raw material cold wall tank of 70 DEG C from design temperature, through transferpump, single tube reactor top is transported to by quantitative 370 gram/minute, reactor wall is overflowed to after being full of feed chamber, feedstock pump uses Frequency Converter Control saturated fatty isopropyl propionate flow to be that the chuck water temperature of sulfonation reactor outside is 80 DEG C.Liquid SO
2through gasification, control, in 65 gram/minute, to enter converter and be converted into SO through mass-flow gas meter
3(transformation efficiency generally reaches 98%), and by Dilution air SO
3, make SO
3volume-fraction concentration in gas is 5%, makes saturated isopropyl fatty acid ester and SO in sulfonation
3between mol ratio be 1.20(± 0.02).SO
3absorb with saturated fatty isopropyl propionate contact reacts, acid product flows out from the bottom of gas-liquid separator, after question response system stability, obtains alpha-sulfonated fatty isopropyl propionate 300g in 5L beaker.
(2) aging: to get 2000g chlorination lard and mix with alpha-sulfonated fatty isopropyl propionate and be placed in aging tank, be incubated under aging tank chuck water temperature is 90 DEG C of conditions and stir 20 minutes, carrying out aging reaction, obtaining aging alpha-sulfonated fatty isopropyl propionate.
(3) decolour: adding 5g hydrogen peroxide through aging alpha-sulfonated fatty isopropyl propionate, and at 90 DEG C, mixing continues to stir, and decolours 20 minutes.
(4) adjust ph: the temperature of the alpha-sulfonated fatty isopropyl propionate after decolouring is reduced to about 40-45 DEG C, it is 8.0 that alpha-sulfonated fatty isopropyl propionate is neutralized to pH by interpolation neutralizing agent 16% potassium hydroxide aqueous solution, in N-process, temperature controls do not surpassing 50 DEG C, finally obtains the alpha-sulfonated fatty isopropyl propionate that reddish-brown is liquid.The configuration 1:9 aqueous solution 24 hours not oil slick.When being applied to leather greasing, have excellent fillibility, leather hand feeling can be made plentiful, and leather surface is smooth.
embodiment 4:
The present embodiment employing R1 carbochain is the saturated fatty acetoacetic ester of C18 is raw material.
(1) sulfonation: use gas phase falling film sulfonation/sulfation laboratory equipment, saturated fatty acetoacetic ester is the raw material cold wall tank of 50 DEG C from design temperature, through transferpump, single tube reactor top is transported to by quantitative 254 gram/minute, reactor wall is overflowed to after being full of feed chamber, feedstock pump uses Frequency Converter Control saturated fatty acetoacetic ester flow to be that the chuck water temperature of sulfonation reactor outside is 60 DEG C.Liquid SO
2through gasification, control, in 65 gram/minute, to enter converter and be converted into SO through mass-flow gas meter
3(transformation efficiency generally reaches 98%), and by Dilution air SO
3, make SO
3volume-fraction concentration in gas is 7%, makes saturated fatty-acid ethyl ester and SO in sulfonation
3between mol ratio be 0.90(± 0.02).SO
3absorb with saturated fatty acetoacetic ester contact reacts, acid product flows out from the bottom of gas-liquid separator, after question response system stability, obtains alpha-sulfonated fatty acetoacetic ester 500g in 5L beaker.
(2) aging: to get 2000g plam oil and mix with alpha-sulfonated fatty acetoacetic ester and be placed in aging tank, be incubated under aging tank chuck water temperature is 70 DEG C of conditions and stir 40 minutes, carrying out aging reaction, obtaining aging alpha-sulfonated fatty acetoacetic ester.
(3) decolour: adding 25g hydrogen peroxide through aging alpha-sulfonated fatty acetoacetic ester, and at 70 DEG C, mixing continues to stir, and decolours 40 minutes.
(4) adjust ph: the temperature of the alpha-sulfonated fatty acetoacetic ester after decolouring is reduced to about 40-45 DEG C, it is 6.0 that alpha-sulfonated fatty acetoacetic ester is neutralized to pH by interpolation neutralizing agent 16% aqueous sodium hydroxide solution, in N-process, temperature controls do not surpassing 50 DEG C, finally obtains the alpha-sulfonated fatty acetoacetic ester that reddish-brown is liquid.The configuration 1:9 aqueous solution 24 hours not oil slick.When being applied to leather greasing, have excellent fillibility, leather hand feeling can be made plentiful, and leather surface is smooth.
comparative example 1
The saturated fatty acid methyl ester that the present embodiment adopts R1 carbochain is the saturated fatty acid methyl ester of C12, R1 carbochain is C14 saturated fatty acid methyl ester, R1 carbochain is C16 and R1 carbochain are the mixture of the saturated fatty acid methyl ester of C18 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 that the saturated fatty acid methyl ester of C16 accounts for 33%; R1 carbochain is that the saturated fatty acid methyl ester of C18 accounts for 17%.
(1) sulfonation: use gas phase falling film sulfonation/sulfation laboratory equipment, saturated fatty acid methyl ester is the raw material cold wall tank of 55 DEG C from design temperature, through transferpump, single tube reactor top is transported to by quantitative 250 gram/minute, reactor wall is overflowed to after being full of feed chamber, feedstock pump uses Frequency Converter Control saturated fatty acid methyl ester flow to be that the chuck water temperature of sulfonation reactor outside is 70 DEG C.Liquid SO
2through gasification, control, in 65 gram/minute, to enter converter and be converted into SO through mass-flow gas meter
3(transformation efficiency generally reaches 98%), and by Dilution air SO
3, gas makes its volume fraction be 6%, makes saturated fatty acid methyl ester and SO in sulfonation
3between mol ratio be 1.15(± 0.02).SO
3absorb with saturated fatty acid methyl ester contact reacts, 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.
(2) get 2000g meal kitchen refiltered oil to mix with alpha-sulfonated fatty acid methyl esters.
(3) decolour: in meal kitchen refiltered oil and alpha-sulfonated fatty acid mixtures of methyl esters, add 20g hydrogen peroxide, and at 85 DEG C, mixing continues to stir, and decolours 30 minutes.
(4) adjust ph: the temperature of the alpha-sulfonated fatty acid methyl esters after decolouring is reduced to about 40-45 DEG C, it is 7.5 that alpha-sulfonated fatty acid methyl esters is neutralized to pH by interpolation neutralizing agent 16% aqueous sodium hydroxide solution, in N-process, temperature controls do not surpassing 50 DEG C, finally obtains the alpha-sulfonated fatty acid methyl esters that reddish-brown is liquid.Within 24 hours, there is oil slick in the configuration 1:9 aqueous solution.
The present invention can summarize with other the specific form without prejudice to spirit of the present invention or principal character.Above-mentioned embodiment of the present invention all can only be thought explanation of the present invention instead of restriction.Therefore every above embodiment is done according to flesh and blood of the present invention any trickle amendment, equivalent variations and modification, all belong in the scope of technical solution of the present invention.