CN101830834A - Preparation method of sulfited fatty acid ester leather fatliquoring agent - Google Patents
Preparation method of sulfited fatty acid ester leather fatliquoring agent Download PDFInfo
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- CN101830834A CN101830834A CN201010174934A CN201010174934A CN101830834A CN 101830834 A CN101830834 A CN 101830834A CN 201010174934 A CN201010174934 A CN 201010174934A CN 201010174934 A CN201010174934 A CN 201010174934A CN 101830834 A CN101830834 A CN 101830834A
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Abstract
The invention relates to a preparation method of a sulfited fatty acid ester leather fatliquoring agent, which comprises the steps of reacting fatty alcohol with maleic anhydride to obtain fatty alcohol maleic acid monoesters; then, reacting long-chain fatty acid and polylol with the fatty alcohol maleic acid monoesters to obtain polyhydroxy alcohol fatty acid ester; and reacting the polyhydroxy alcohol fatty acid ester with sulfite to obtain sulfited polyhydroxy alcohol fatty acid ester which is modified with water, and preparing leather fatliquors. The preparation method has the advantages of simple process, mild reaction conditions, and no discharge of waste water, waste gas and waste slag in the synthetic process.
Description
Technical field
The invention belongs to the leather chemical industry technical field, relate to a kind of preparation method of leather fat, be specifically related to a kind of preparation method of sulfited fatty acid ester leather fatliquoring agent.
Background technology
Fatting agent is a class leather chemical industry material of consumption maximum in the process hides process, by the stuffing operation stuffing material is introduced in the leather, be evenly distributed in the collegen filament surface of leather, collegen filament are separated, boning between the collegen filament after the dry dehydration in order to prevent leather, increase the oilness between the collegen filament, prevent to remove from office hardening and become fragile, make leather soft, anti-bending, have a water resisting property, improve the physical and mechanical properties of leather.
In recent years, along with the raising of leather products class, people also have higher requirement to leather greasing, except fundamental propertys such as stuffing leather is soft comfortable, also require the stuffing leather in use not produce performances such as peculiar smell, photostabilization are good.Traditional leather fat is that raw material is made with natural animal-plant oil mainly, and the component complexity of natural animal-plant oil, bad saturation ratio height causes leather to produce peculiar smell, and anti-yellowing property reduces.
The chemical property of mineral oil and synthetic ester is stable, be that the emulsification and the penetrating power of raw material synthetic leather fat is strong with it, is used for leather greasing and can gives stuffing and remove from office good physical and mechanical properties.With mineral oil or synthetic ester is that raw material synthetic leather fatting agent has following several method usually: 1) adopt Sulphurex process that molecular weight is directly carried out sulfonation at 300～400 whiteruss; 2) with the long chain aliphatic alcohol be raw material, synthetic by methods such as sulfation, sulfonation maleinization and phosphorylations; 3) with the longer chain fatty acid be raw material, obtain fatty acid ester, make corresponding leather fat through modified methods such as sulphiting, sulfonation, sulfation and phosphorylations then with polyoxyethylene glycol or polyol reaction.But the facility investment of Sulphurex process is big, and the stability of emulsion and the package stability of the leather fat that sulfonation maleinization method makes are relatively poor.
Summary of the invention
In order to overcome above-mentioned problems of the prior art, the purpose of this invention is to provide a kind of preparation method of sulfited fatty acid ester leather fatliquoring agent, the stability of emulsion of the fatting agent that makes and excellent storage stability, and production technique is simple, and facility investment is little.
The technical solution adopted in the present invention is, a kind of preparation method of sulphiting lipid acid leather fat, Fatty Alcohol(C12-C14 and C12-C18) and maleic anhydride reaction are obtained Fatty Alcohol(C12-C14 and C12-C18) toxilic acid monoesters, then, longer chain fatty acid, polyvalent alcohol and the reaction of this Fatty Alcohol(C12-C14 and C12-C18) toxilic acid monoesters are obtained polyol esters of fatty acids, again this polyol esters of fatty acids and sulphite reaction are obtained the sulphiting polyol esters of fatty acids, carry out water and regulate, make leather fat, this preparation method specifically carries out according to the following steps:
Step 1: press amount than 1: 1～1.1, get Fatty Alcohol(C12-C14 and C12-C18) and maleic anhydride respectively, maleic anhydride is warming up to 55 ℃～60 ℃, then, under whipped state, Fatty Alcohol(C12-C14 and C12-C18) is splashed in 20min～30min in the maleic anhydride of fusing, after dropwising, under 75 ℃～100 ℃ temperature, reaction 2h～4h makes Fatty Alcohol(C12-C14 and C12-C18) toxilic acid monoesters;
Step 2: press amount than 1: 1: 1, get the Fatty Alcohol(C12-C14 and C12-C18) toxilic acid monoesters that longer chain fatty acid, polyvalent alcohol and step 1 make respectively, the anabolic reaction thing, an acidic catalyst is added in this reactant again, the quality of this an acidic catalyst accounts for 0.1%～1% of reactant total mass, place the environment of 110 ℃～140 ℃ of vacuum tightness 0.01MPa～0.05MPa, temperature, reaction 2h～6h, obtain fatty acid polyol ester;
Step 3: press amount than 1～1.1: 1, get the polyol esters of fatty acids that sodium bisulfite and step 2 make respectively, it is in 55 ℃～60 ℃ the water that sodium bisulfite is dissolved in temperature, form the bisulfite saturated aqueous solution of sodium, it is in 70 ℃～75 ℃ the polyol esters of fatty acids that this saturated aqueous solution is added temperature, then, under 90 ℃～110 ℃ temperature, reaction 3h～6h generates the sulphiting polyol esters of fatty acids, and resultant is cooled to 65 ℃～75 ℃, the adding temperature is 55 ℃～60 ℃ a water, to working substance content be 60%～70%, under the normal temperature, make leather fat.
Preparation method of the present invention is a raw material with Fatty Alcohol(C12-C14 and C12-C18), maleic anhydride, longer chain fatty acid and sulphite, reaction under certain condition obtains polyol esters of fatty acids, carrying out water again regulates, make leather fat, the synthesis technique of this method is simple, and facility investment is little, the reaction conditions gentleness, there is not " three wastes " discharging in the building-up process, the stability of emulsion of the leather fat that makes and excellent storage stability.
Embodiment
The present invention is described in detail below in conjunction with embodiment.
Leather fat preparation method of the present invention, Fatty Alcohol(C12-C14 and C12-C18) and maleic anhydride reaction are obtained Fatty Alcohol(C12-C14 and C12-C18) toxilic acid monoesters, then, with longer chain fatty acid, polyvalent alcohol is (as ethylene glycol, 1,2-butyleneglycol etc.) react under certain condition and obtain polyol esters of fatty acids with this Fatty Alcohol(C12-C14 and C12-C18) toxilic acid monoesters, again this polyol esters of fatty acids and sulphite reaction are obtained the sulphiting polyol esters of fatty acids, and carry out water and regulate, make leather fat, this preparation method synthesis technique is simple, the reaction conditions gentleness, and do not have " three wastes " discharging in the building-up process, this method is specifically carried out according to the following steps:
Step 1: press amount than 1: 1～1.1, get Fatty Alcohol(C12-C14 and C12-C18) and maleic anhydride respectively, maleic anhydride is warming up to 55～60 ℃, makes its fusing, then, under whipped state, in 20～30min, Fatty Alcohol(C12-C14 and C12-C18) is splashed in the maleic anhydride of fusing, after dropwising, liquation is warming up to 75～100 ℃ (preferred 85 ℃), reaction 2～4h (preferred 3h) makes Fatty Alcohol(C12-C14 and C12-C18) toxilic acid monoesters;
Fatty Alcohol(C12-C14 and C12-C18) adopts a kind of in C4 to the C12 Fatty Alcohol(C12-C14 and C12-C18).More suitable Fatty Alcohol(C12-C14 and C12-C18) has amylalcohol, primary isoamyl alcohol, n-Octanol, isooctyl alcohol, propyl carbinol and lauryl alcohol etc.
Step 2: press amount than 1: 1: 1, get the Fatty Alcohol(C12-C14 and C12-C18) toxilic acid monoesters that longer chain fatty acid, polyvalent alcohol and step 1 make respectively, the anabolic reaction thing, an acidic catalyst is added in this reactant again, the quality of this an acidic catalyst accounts for 0.1～1% of reactant total mass, then, places the environment of 110～140 ℃ of vacuum tightness 0.01～0.05MPa, temperature, reaction 2～6h, the obtain fatty acid polyol ester;
Longer chain fatty acid adopts a kind of in C12 to the C18 longer chain fatty acid.More suitable longer chain fatty acid has laurostearic acid, TETRADECONIC ACID, palmitic acid, stearic acid, octadecenic acid, oleic acid and stearic acid.
Polyvalent alcohol adopts a kind of in a kind of or C2 to the C6 trivalent alcohol in C2 to the C6 dibasic alcohol, as ethylene glycol, 1, and 2-butyleneglycol, 1,4-butyleneglycol, glycerol, hexylene glycol.More suitable have ethylene glycol and 1, a 2-butyleneglycol.
An acidic catalyst employing tosic acid or concentration are 98% the vitriol oil, preferred tosic acid.
Step 3: press amount than 1～1.1: 1, get the polyol esters of fatty acids that sodium bisulfite and step 2 make respectively, it is in 55～60 ℃ the water that sodium bisulfite is dissolved in temperature, form the bisulfite saturated aqueous solution of sodium, after polyol esters of fatty acids is heated to 70～75 ℃, the bisulfite saturated aqueous solution of sodium is added wherein, then, and under 90～110 ℃ temperature, reaction 3～6h, generate the sulphiting polyol esters of fatty acids, this sulphiting polyol esters of fatty acids is cooled to 65～75 ℃, and the water that adds temperature and be 55～60 ℃ is regulated, to working substance content be 60～70%, the normal temperature discharging makes leather fat.
Comprise the sulphiting polyol esters of fatty acids in the leather fat that adopts the inventive method to make, the schematic structure of this sulphiting polyol esters of fatty acids is:
In the formula: R
1Be C
11-17Chain alkyl; R
2Be C
4-12Alkyl; N=2～6.
Contain hydrophilic radical-SO on the molecule of above-mentioned sulphiting polyol esters of fatty acids
3Na, this group has good emulsifying ability and penetrating power, when being used for leather greasing, can give leather soft comfort feel.
Preparation method of the present invention obtains polyhydric alcohol fatty acid ester by longer chain fatty acid, Fatty Alcohol(C12-C14 and C12-C18) toxilic acid monoesters and polyol reaction, two keys have been introduced on the molecule of this polyhydric alcohol fatty acid ester, then, polyhydric alcohol fatty acid ester and sulphite are carried out sulfited reaction, on the molecule of first alcohol fatty acid ester, introduce hydrophilic radical-SO
3Na obtains purpose product sulfited fatty acid ester.Chemical reaction mechanism among this preparation method is as follows:
The first step, Fatty Alcohol(C12-C14 and C12-C18) maleic acid ester synthetic
Second step, polyol esters of fatty acids synthetic
The 3rd step, sulfurous acid fatty acid ester synthetic
In the formula: R
1Be the alkyl of C5-12, R
2Be the chain alkyl of C11-17, n is 2～6 integer.
Contain hydrophilic radical-SO in the leather fat of the present invention
3Na has good emulsifying capacity and penetrating power, and porous is evenly distributed in the leather fiber surface to the leather depths, makes the stuffing leather very soft.
Embodiment 1
Press amount than 1: 1, get amylalcohol and maleic anhydride respectively, maleic anhydride is heated to 55～60 ℃, makes its fusing, then, under whipped state, amylalcohol is splashed in 20～30min in the maleic anhydride of fusing, dropwise, liquation is warming up to 75 ℃, reaction 4h makes amylalcohol toxilic acid monoesters; Press amount than 1: 1: 1, the amylalcohol toxilic acid monoesters of getting stearic acid, ethylene glycol respectively and making, the anabolic reaction thing, getting concentration again and be 98% the vitriol oil adds in this reactant, the quality of the vitriol oil accounts for 0.1% of this reactant total mass, then, places the environment of 110 ℃ of vacuum tightness 0.01Mpa, temperature, reaction 6h makes stearic acid amylalcohol toxilic acid monoesters diethylene glycol dilaurate; Press amount than 1: 1, the stearic acid amylalcohol toxilic acid monoesters diethylene glycol dilaurate of getting sodium bisulfite respectively and making, it is in 55 ℃ the water that sodium bisulfite is dissolved in temperature, form the bisulfite saturated aqueous solution of sodium, after stearic acid amylalcohol toxilic acid monoesters diethylene glycol dilaurate is heated to 70 ℃, add the bisulfite saturated aqueous solution of sodium, under 90 ℃ temperature, reaction 6h generates sulphiting stearic acid amylalcohol toxilic acid monoesters diethylene glycol dilaurate, then, the sulphiting stearic acid amylalcohol toxilic acid monoesters diethylene glycol dilaurate that generates is cooled to 65 ℃, adds temperature and be 55 ℃ water, to effective solid content be 60%, under the normal temperature, make leather fat.
Embodiment 2
Press amount than 1: 1.1, get isooctyl alcohol and maleic anhydride respectively, maleic anhydride is warming up to 55～60 ℃, makes its fusing, then, under whipped state, isooctyl alcohol is splashed in 20～30min in the maleic anhydride of fusing, after dropwising, liquation is warming up to 100 ℃, reaction 2h makes isooctyl alcohol toxilic acid monoesters; Press amount than 1: 1: 1, get TETRADECONIC ACID, 1 respectively, 2-butyleneglycol and the isooctyl alcohol toxilic acid monoesters that makes, the anabolic reaction thing adds tosic acid in this reactant, the quality of tosic acid accounts for 1% of this reactant total mass, then, place the environment of 140 ℃ of vacuum tightness 0.05Mpa, temperature, reaction 2h, make TETRADECONIC ACID isooctyl alcohol toxilic acid monoesters 1,2-butyleneglycol dibasic acid esters; Press amount than 1.1: 1, the TETRADECONIC ACID isooctyl alcohol toxilic acid monoesters 1 of getting sodium bisulfite respectively and making, 2-butyleneglycol dibasic acid esters, it is in 60 ℃ the water that sodium bisulfite is dissolved in temperature, form the bisulfite saturated aqueous solution of sodium, with TETRADECONIC ACID isooctyl alcohol toxilic acid monoesters 1, after 2-butyleneglycol dibasic acid esters is heated to 75 ℃, add the bisulfite saturated aqueous solution of sodium, under 110 ℃ temperature, reaction 3h, generate sulphiting TETRADECONIC ACID isooctyl alcohol toxilic acid monoesters 1,2-butyleneglycol dibasic acid esters, with the sulphiting TETRADECONIC ACID isooctyl alcohol toxilic acid monoesters 1 that generates, 2-butyleneglycol dibasic acid esters is cooled to 75 ℃, the adding temperature is that 60 ℃ water is regulated, to working substance content be 70%, be cooled to normal temperature, make leather fat.
Embodiment 3
Press amount than 1: 1.05, get n-Octanol and maleic anhydride respectively, maleic anhydride is warming up to 55～60 ℃, makes its fusing, then, under whipped state, n-Octanol is splashed in 20～30min in the maleic anhydride of fusing, after dropwising, liquation is warming up to 85 ℃, reaction 3h makes n-Octanol toxilic acid monoesters; Press amount than 1: 1: 1, the n-Octanol toxilic acid monoesters of getting octadecenic acid, glycerol respectively and making, the anabolic reaction thing, with concentration is that 98% the vitriol oil adds in this reactant, the quality of the vitriol oil accounts for 0.55% of this reactant total mass, then, places the environment of 125 ℃ of vacuum tightness 0.03Mpa, temperature, reaction 4h makes octadecenic acid n-Octanol toxilic acid glycerol dibasic ester; Press amount than 1.05: 1, the octadecenic acid n-Octanol toxilic acid glycerol dibasic ester of getting sodium bisulfite respectively and making, it is in 58 ℃ the water that sodium bisulfite is dissolved in temperature, form the bisulfite saturated aqueous solution of sodium, after octadecenic acid n-Octanol toxilic acid glycerol dibasic ester is heated to 72 ℃, add the bisulfite saturated aqueous solution of sodium, under 100 ℃ temperature, reaction 4.5h, generate sulphiting octadecenic acid n-Octanol toxilic acid glycerol dibasic ester, the sulphiting octadecenic acid n-Octanol toxilic acid glycerol dibasic ester that generates is cooled to 70 ℃, the adding temperature is that 58 ℃ water is regulated, to working substance content be 65%, be cooled to normal temperature, make leather fat.
Embodiment 4
Press amount than 1: 1.01, get primary isoamyl alcohol and maleic anhydride respectively, maleic anhydride is warming up to 55～60 ℃, makes its fusing, then, under whipped state, in 20～30min, primary isoamyl alcohol is splashed in the maleic anhydride of fusing, after dropwising, liquation is warming up to 80 ℃, reaction 3h makes primary isoamyl alcohol toxilic acid monoesters; Press amount than 1: 1: 1, the primary isoamyl alcohol toxilic acid monoesters of getting palmitic acid, hexylene glycol respectively and making, the anabolic reaction thing, tosic acid is added in this reactant, the quality of tosic acid accounts for 0.2% of reactant total mass, then, places the environment of 115 ℃ of vacuum tightness 0.02MPa, temperature, reaction 5h makes palmitic acid primary isoamyl alcohol toxilic acid hexylene glycol dibasic acid esters; Press amount than 1.01: 1, the palmitic acid primary isoamyl alcohol toxilic acid hexylene glycol dibasic acid esters of getting sodium bisulfite respectively and making, it is in 56 ℃ the water that sodium bisulfite is dissolved in temperature, form the bisulfite saturated aqueous solution of sodium, it is in 71 ℃ the palmitic acid primary isoamyl alcohol toxilic acid hexylene glycol dibasic acid esters that this saturated aqueous solution is added temperature, then, under 95 ℃ temperature, reaction 5.5h generates palmitic acid primary isoamyl alcohol toxilic acid hexylene glycol dibasic acid esters, and resultant is cooled to 66 ℃, the adding temperature is that 56 ℃ water is regulated, to working substance content be 62%, the normal temperature discharging makes leather fat.
Embodiment 5
Press amount than 1: 1.09, get lauryl alcohol and maleic anhydride respectively, maleic anhydride is warming up to 55～60 ℃, makes its fusing, then, under whipped state, in 20～30min, this mixture is splashed in the maleic anhydride of fusing, after dropwising, liquation is warming up to 90 ℃, reaction 2.5h makes lauryl alcohol toxilic acid monoesters; Press amount than 1: 1: 1, get laurostearic acid, 1 respectively, 4-butyleneglycol and the lauryl alcohol toxilic acid monoesters that makes, the anabolic reaction thing adds tosic acid in this reactant again, the quality of tosic acid accounts for 0.9% of this reactant total mass, then, place the environment of 135 ℃ of vacuum tightness 0.04MPa, temperature, reaction 3.5h, make laurostearic acid lauryl alcohol toxilic acid 1,4-butyleneglycol dibasic acid esters; Press amount than 1.09: 1, the laurostearic acid lauryl alcohol toxilic acid 1 of getting sodium bisulfite respectively and making, 4-butyleneglycol dibasic acid esters, it is in 59 ℃ the water that sodium bisulfite is dissolved in temperature, form the bisulfite saturated aqueous solution of sodium, it is 74 ℃ laurostearic acid lauryl alcohol toxilic acid 1 that this saturated aqueous solution is added temperature, in the 4-butyleneglycol dibasic acid esters, then, under 105 ℃ temperature, reaction 4h generates sulphiting laurostearic acid lauryl alcohol toxilic acid 1,4-butyleneglycol dibasic acid esters, this resultant is cooled to 74 ℃, and the water that adds temperature and be 59 ℃ is regulated, to working substance content be 69%, the normal temperature discharging makes leather fat.
Embodiment 6
98g maleic anhydride (1mol) adding is equipped with in the dry four-hole glass flask of agitator and prolong, is warmed up to 55～60 ℃, make it fusing.Under whipped state, in 20～30min, drip isooctyl alcohol 136.5g (1.05mol) then, after dropwising, be warmed up to 80 ℃ of reaction 3.0h, obtain isooctyl alcohol toxilic acid monoesters; In the there-necked flask with oleic acid 56.8g (0.2mol), ethylene glycol 12.4g (0.2mol), tosic acid 0.574g and isooctyl alcohol toxilic acid monoesters 45.6g (0.2mol) adding band reliever that makes and agitator, under temperature is 120 ℃, the condition of vacuum tightness 0.02MPa, react 3h, be cooled to 70 ℃.It is in 55 ℃ the warm water that sodium bisulfite 26.5g (0.21mol) is dissolved in the 50g temperature, forms the bisulfite saturated aqueous solution of sodium, then, this saturated aqueous solution is added reactor, insulation back flow reaction 4h under 90 ℃ of temperature.After reaction finished, adding 44.2g temperature was 55 ℃ a warm water in the product that generates, and regulating working substance content is 60%, reduces to the normal temperature discharging, makes the transparent liquid leather fat of reddish-brown.
Embodiment 7
The isooctyl alcohol toxilic acid monoesters 45.6g (0.2mol) that makes among stearic acid 57.2g (0.2mol), ethylene glycol 12.4g (0.2mol), tosic acid 0.574g and the embodiment 6 is added in the there-necked flask of band reliever and agitator, under temperature is 120 ℃, the condition of vacuum tightness 0.02Mpa, react 3h, be cooled to 70 ℃.It is in 60 ℃ the warm water that sodium bisulfite 26.5g (0.21mol) is dissolved in the 50g temperature, forms the bisulfite saturated aqueous solution of sodium, then, this saturated aqueous solution is added reactor, under 90 ℃ temperature, and insulation back flow reaction 4h.After reaction finishes, add the 44.2g temperature and be 60 ℃ warm water in resultant, regulating working substance content is 60%, and cooling discharge makes the leather fat of white pulpous state.
Embodiment 8
98g maleic anhydride (1mol) adding is equipped with in the dry four-hole glass flask of agitator and prolong, is warmed up to 55～60 ℃, make it fusing.Under whipped state, to wherein dripping primary isoamyl alcohol 92.4g (1.05mol), after dropwising, be warmed up to 80 ℃ in 20～30min then, reaction 3.0h obtains primary isoamyl alcohol toxilic acid monoesters.In the there-necked flask with TETRADECONIC ACID 45.6g (0.2mol), butyleneglycol 18g (0.2mol), tosic acid 0.504g and primary isoamyl alcohol toxilic acid monoesters 37.2g (0.2mol) adding band reliever that makes and agitator, under the condition of temperature, react 3h, be cooled to 70 ℃ for 120 ℃ of temperature, vacuum tightness 0.02Mpa.It is in 57.5 ℃ the warm water that sodium bisulfite 26.5g (0.21mol) is dissolved in the 50g temperature, forms the bisulfite saturated aqueous solution of sodium, then, this saturated aqueous solution is added reactor, under 90 ℃ temperature, and insulation back flow reaction 4h.After reaction finishes, add the 34.8g temperature and be 57.5 ℃ warm water in resultant, regulating working substance content is 60%, and cooling discharge makes the leather fat of white pulpous state.
Embodiment 9
The primary isoamyl alcohol toxilic acid monoesters 37.2g (0.2mol) that makes among laurostearic acid 40g (0.2mol), butyleneglycol 18g (0.2mol), tosic acid 0.504g and the embodiment 8 is added in the there-necked flask of band reliever, agitator, under temperature is 120 ℃, the condition of vacuum tightness 0.02Mpa, react 3h, be cooled to 70 ℃.It is in 56 ℃ the warm water that sodium bisulfite 26.5g (0.21mol) is dissolved in the 50g temperature, forms the bisulfite saturated aqueous solution of sodium, then, this saturated aqueous solution is added reactor, insulation back flow reaction 4h under 90 ℃ temperature.After reaction finishes, add the 31.3g temperature and be 56 ℃ warm water in resultant, regulating working substance content is 60%, and the normal temperature discharging makes the leather fat of white pulpous state.
Embodiment 10
98g maleic anhydride (1mol) adding is equipped with in the dry four-hole glass flask of agitator, prolong, is warmed up to 55～60 ℃, make it fusing.Under whipped state, about 20～30min,, after dropwising, under 80 ℃ temperature, react 3.0h then, obtain propyl carbinol toxilic acid monoesters to wherein dripping propyl carbinol 74g (1.05mol).Oleic acid 56.8g (0.2mol), hexylene glycol 23.6g (0.2mol), tosic acid 0.574g and the propyl carbinol toxilic acid monoesters 34.4g (0.2mol) that makes are added in the there-necked flask of band reliever, agitator, under temperature is 120 ℃, the condition of vacuum tightness 0.02Mpa, react 3h, be cooled to 70 ℃.It is in 59 ℃ the warm water that sodium bisulfite 26.5g (0.21mol) is dissolved in the 50g temperature, forms the bisulfite saturated aqueous solution of sodium, then, this saturated aqueous solution is added in reactor insulation back flow reaction 4h under 90 ℃ temperature.After reaction finished, adding 10.5g temperature was 59 ℃ a warm water in resultant, and regulating working substance content is 70%, and the normal temperature discharging makes the transparent liquid leather fat of reddish-brown.
Embodiment 11
The propyl carbinol toxilic acid monoesters 34.4g (0.2mol) that stearic acid 57.2g (0.2mol), hexylene glycol 23.6g (0.2mol), tosic acid 0.574g and embodiment 10 are made adds in the there-necked flask of band reliever, agitator, under temperature is 120 ℃, the condition of vacuum tightness 0.02Mpa, react 3h, be cooled to 70 ℃.It is in 60 ℃ the warm water that sodium bisulfite 26.5g (0.21mol) is dissolved in the 50g temperature, forms the bisulfite saturated aqueous solution of sodium, then, this saturated aqueous solution is added reactor, insulation back flow reaction 4h under 90 ℃ temperature.After reaction finishes, add the 10.7g temperature and be 60 ℃ warm water in resultant, regulating working substance content is 70%, and the normal temperature discharging makes the leather fat of white paste.
Claims (10)
1. the preparation method of a sulphiting lipid acid leather fat, Fatty Alcohol(C12-C14 and C12-C18) and maleic anhydride reaction are obtained Fatty Alcohol(C12-C14 and C12-C18) toxilic acid monoesters, then, longer chain fatty acid, polyvalent alcohol and the reaction of this Fatty Alcohol(C12-C14 and C12-C18) toxilic acid monoesters are obtained polyol esters of fatty acids, again this polyol esters of fatty acids and sulphite reaction are obtained the sulphiting polyol esters of fatty acids, carry out water and regulate, make leather fat, it is characterized in that this preparation method specifically carries out according to the following steps:
Step 1: press amount than 1: 1～1.1, get Fatty Alcohol(C12-C14 and C12-C18) and maleic anhydride respectively, maleic anhydride is warming up to 55 ℃～60 ℃, then, under whipped state, Fatty Alcohol(C12-C14 and C12-C18) is splashed in 20min～30min in the maleic anhydride of fusing, after dropwising, under 75 ℃～100 ℃ temperature, reaction 2h～4h makes Fatty Alcohol(C12-C14 and C12-C18) toxilic acid monoesters;
Step 2: press amount than 1: 1: 1, get the Fatty Alcohol(C12-C14 and C12-C18) toxilic acid monoesters that longer chain fatty acid, polyvalent alcohol and step 1 make respectively, the anabolic reaction thing, an acidic catalyst is added in this reactant again, the quality of this an acidic catalyst accounts for 0.1%～1% of reactant total mass, place the environment of 110 ℃～140 ℃ of vacuum tightness 0.01MPa～0.05MPa, temperature, reaction 2h～6h, obtain fatty acid polyol ester;
Step 3: press amount than 1～1.1: 1, get the polyol esters of fatty acids that sodium bisulfite and step 2 make respectively, it is in 55 ℃～60 ℃ the water that sodium bisulfite is dissolved in temperature, form the bisulfite saturated aqueous solution of sodium, it is in 70 ℃～75 ℃ the polyol esters of fatty acids that this saturated aqueous solution is added temperature, then, under 90 ℃～110 ℃ temperature, reaction 3h～6h generates the sulphiting polyol esters of fatty acids, and resultant is cooled to 65 ℃～75 ℃, the adding temperature is 55 ℃～60 ℃ a water, to working substance content be 60%～70%, under the normal temperature, make leather fat.
2. according to the preparation method of the described leather fat of claim 1, it is characterized in that this preparation method carries out according to the following steps:
Step 1: press amount than 1: 1～1.1, get Fatty Alcohol(C12-C14 and C12-C18) and maleic anhydride respectively, maleic anhydride is warming up to 55 ℃～60 ℃, then, under whipped state, Fatty Alcohol(C12-C14 and C12-C18) is splashed in 20min～30min in the maleic anhydride of fusing, after dropwising, under 85 ℃ temperature, reaction 3h makes Fatty Alcohol(C12-C14 and C12-C18) toxilic acid monoesters;
Step 2: press amount than 1: 1: 1, get the Fatty Alcohol(C12-C14 and C12-C18) toxilic acid monoesters that longer chain fatty acid, polyvalent alcohol and step 1 make respectively, the anabolic reaction thing, an acidic catalyst is added in this reactant, the quality of this an acidic catalyst accounts for 0.1%～1% of reactant total mass, then, places the environment of 110 ℃～140 ℃ of vacuum tightness 0.01MPa～0.05MPa, temperature, reaction 2h～6h, the obtain fatty acid polyol ester;
Step 3: press amount than 1～1.1: 1, get the polyol esters of fatty acids that sodium bisulfite and step 2 make respectively, it is in 55 ℃～60 ℃ the water that sodium bisulfite is dissolved in temperature, form the bisulfite saturated aqueous solution of sodium, it is in 70 ℃～75 ℃ the polyol esters of fatty acids that this saturated aqueous solution is added temperature, then, under 90 ℃～110 ℃ temperature, reaction 3h～6h generates the sulphiting polyol esters of fatty acids, and resultant is cooled to 65 ℃～75 ℃, the adding temperature is 55 ℃～60 ℃ a water, to working substance content be 60%～70%, under the normal temperature, make leather fat.
3. according to the preparation method of claim 1 or 2 described leather fats, it is characterized in that Fatty Alcohol(C12-C14 and C12-C18) in the described step 1 adopts a kind of in C4 to the C12 Fatty Alcohol(C12-C14 and C12-C18).
4. according to the preparation method of the described leather fat of claim 3, it is characterized in that described C4 to C12 Fatty Alcohol(C12-C14 and C12-C18) is amylalcohol, primary isoamyl alcohol, n-Octanol, isooctyl alcohol, lauryl alcohol or propyl carbinol.
5. according to the preparation method of claim 1 or 2 described leather fats, it is characterized in that longer chain fatty acid in the described step 2 adopts a kind of in C12 to the C18 longer chain fatty acid.
6. according to the preparation method of the described leather fat of claim 5, it is characterized in that described C12 to C18 longer chain fatty acid is laurostearic acid, TETRADECONIC ACID, palmitic acid, stearic acid, octadecenic acid, oleic acid or stearic acid.
7. according to the preparation method of claim 1 or 2 described leather fats, it is characterized in that polyvalent alcohol in the described step 2 adopts a kind of in a kind of or C2 to the C6 trivalent alcohol in C2 to the C6 dibasic alcohol.
8. according to the preparation method of the described leather fat of claim 7, it is characterized in that described C2 to C6 dibasic alcohol adopts ethylene glycol, 1,2-butyleneglycol, 1,4-butyleneglycol or hexylene glycol.
9. according to the preparation method of the described leather fat of claim 7, it is characterized in that described C2 to C6 trivalent alcohol adopts glycerol.
10. according to the preparation method of claim 1 or 2 described leather fats, it is characterized in that an acidic catalyst employing tosic acid in the described step 2 or concentration are 98% the vitriol oil.
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| CN102399916A (en) * | 2011-10-17 | 2012-04-04 | 深圳市天之一科技开发有限公司 | Process for preparing fat-liquoring agent by hogwash oil |
| CN106170565A (en) * | 2014-01-16 | 2016-11-30 | 科瑞臣有限公司 | Polymer fatliquoring agent |
| CN106399600A (en) * | 2016-11-15 | 2017-02-15 | 王鲁燕 | Novel synthetic fatliquor and preparation method thereof |
| CN106631913A (en) * | 2016-11-15 | 2017-05-10 | 王鲁燕 | Novel gloss oil-resistant synthetic fatliquoring agent and preparation method thereof |
| CN106866472A (en) * | 2017-01-04 | 2017-06-20 | 温州大学 | A kind of polymer fatliquoring agent containing sulphite structure and preparation method thereof |
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| CN101698703A (en) * | 2009-10-22 | 2010-04-28 | 厦门大学 | Maleic acid isoalcohol diester and prepration method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102399916A (en) * | 2011-10-17 | 2012-04-04 | 深圳市天之一科技开发有限公司 | Process for preparing fat-liquoring agent by hogwash oil |
| CN106170565A (en) * | 2014-01-16 | 2016-11-30 | 科瑞臣有限公司 | Polymer fatliquoring agent |
| CN106399600A (en) * | 2016-11-15 | 2017-02-15 | 王鲁燕 | Novel synthetic fatliquor and preparation method thereof |
| CN106631913A (en) * | 2016-11-15 | 2017-05-10 | 王鲁燕 | Novel gloss oil-resistant synthetic fatliquoring agent and preparation method thereof |
| CN106866472A (en) * | 2017-01-04 | 2017-06-20 | 温州大学 | A kind of polymer fatliquoring agent containing sulphite structure and preparation method thereof |
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