CN101956030B - Method for preparing succinic acid sulphonated fat-liquoring agent - Google Patents

Method for preparing succinic acid sulphonated fat-liquoring agent Download PDF

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CN101956030B
CN101956030B CN 201010503072 CN201010503072A CN101956030B CN 101956030 B CN101956030 B CN 101956030B CN 201010503072 CN201010503072 CN 201010503072 CN 201010503072 A CN201010503072 A CN 201010503072A CN 101956030 B CN101956030 B CN 101956030B
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polyoxyethylene ether
alcohol
succinic acid
sulphiting
fatty alcohol
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CN101956030A (en
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周中平
龙忠珍
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BROTHER SCIENCE AND TECHNOLOGY Co Ltd
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BROTHER SCIENCE AND TECHNOLOGY Co Ltd
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Abstract

The invention relates to a method for preparing a succinic acid sulphonated fat-liquoring agent, which comprises the following steps of: purifying fatty alcohol-polyoxyethylene ether, then performing esterification reaction and sulphonation reaction on the purified fatty alcohol-polyoxyethylene ether and maleic anhydride to prepare succinic acid sulphonated fatty alcohol-polyoxyethylene ether, adding sulfite vegetable oil into the succinic acid sulphonated fatty alcohol-polyoxyethylene ether to perform compounding, and controlling the succinic acid sulphonated polyoxyethylene ether to be between 30 and 80 percent and the sulfite vegetable oil to be between 20 and 70 percent; and adjusting the content of effective substances to be between 40 and 70 percent by using water so as to obtain the succinic acid sulphonated fatty alcohol-polyoxyethylene ether fat-liquoring agent, succinic acid sulphonated fat-liquoring agent for short. The fat-liquoring agent has good emulsifying capacity, the emulsion has good stability, and 1:9 aqueous emulsion is not demixed in 24 hours; and the leather using the fat-liquoring agent has the advantages of good softness, uniformity and plump property, good elasticity, good light and heat resistance, low atomization value and the like.

Description

A kind of preparation method of succinic acid sulphonated fat-liquoring agent
Technical field
The present invention relates to a kind of preparation method of leather fat, particularly relate to a kind of preparation method of succinic acid sulphonated fat-liquoring agent.
Background technology
It is that starting raw material prepares that traditional succinic acid sulphonated fat-liquoring agent adopts the natural animal-plant grease usually, generally passes through diethanol amide introducing hydroxyl, forms the MALEIC ANHYDRIDE ester with the maleic anhydride reaction again, then through obtaining finished product after the sulfonated reagent sulfonation.The fatting agent that obtains by above technique generally is yellow paste, is difficult for flowing, and the emulsifying water effect is relatively poor, and package stability and light fastness are also all poor.
Fatty alcohol-polyoxyethylene ether mainly is to make by the Fatty Alcohol(C12-C14 and C12-C18) with reactive hydrogen and ethylene oxide polymerization, because itself is with hydrophilic, lipophilic group, the HLB value that the difference of oxyethyl group number is given fatty alcohol-polyoxyethylene ether is different, general as nonionogenic tenside, be widely applied to washing, shampoo, in the industries such as weaving and leather.But the method that adopts fatty alcohol-polyoxyethylene ether to prepare succinic acid sulphonated fat-liquoring agent there is not yet report.
Summary of the invention
The present invention is directed to above-mentioned the deficiencies in the prior art, a kind of preparation method of succinic acid sulphonated fat-liquoring agent has been proposed, this fatting agent has good automatic emulsifying performance, appearance transparent, flowing property and emulsifying water excellent property, can give the characteristic of leather softness, plentiful, good springiness, and make it to have good heat-resisting light fastness.
In order to achieve the above object, the present invention has adopted following technical scheme:
A kind of preparation method of succinic acid sulphonated fat-liquoring agent, described succinic acid sulphonated fat-liquoring agent is by following substances and water is composite forms, in the quality percentage, succsinic acid alpha-sulfonated fatty polyoxyethylenated alcohol 30%~80%, sulphiting vegetables oil 20%~70%; It comprises the steps:
⑴ the preparation of succsinic acid alpha-sulfonated fatty polyoxyethylenated alcohol:
The purification of fatty alcohol-polyoxyethylene ether: at first fatty alcohol-polyoxyethylene ether is added in the reactor, open to stir, open vacuum pump, keep vacuum tightness be-0.03Mpa~-0.1Mpa, be warming up to 100 ℃~180 ℃, be incubated after 0.5~2 hour, lower the temperature for subsequent use;
Sulfonation reaction: in through the fatty alcohol-polyoxyethylene ether that purifies, add maleic anhydride by 1: 0.5~2 mol ratios, be warming up to 60 ℃~130 ℃, reacted 1~8 hour; Then add sulfonated reagent in reaction mass, the mol ratio of control sulfonated reagent and maleic anhydride is 0.5~1: 1, and the control temperature of reaction is 70 ℃~100 ℃, reacts 1~5 hour, obtains succsinic acid alpha-sulfonated fatty polyoxyethylenated alcohol;
⑵ composite: step ⑴ gained succsinic acid alpha-sulfonated fatty polyoxyethylenated alcohol is cooled to 50 ℃~70 ℃, add the sulphiting vegetables oil, in the quality percentage, controlling respectively succsinic acid sulfonation Soxylat A 25-7 is 30%~80%, and the sulphiting vegetables oil is 20%~70%; Then regulate material to pH6.0~8.0 with sodium hydroxide, and water to be adjusted to working substance content be 40%~70%, continue to stir 0.5~1 hour, obtain succsinic acid alpha-sulfonated fatty polyoxyethylenated alcohol fatting agent, be called for short succinic acid sulphonated fat-liquoring agent.
Described fatty alcohol-polyoxyethylene ether is Dodecyl Polyoxyethylene Ether, tetradecyl alcohol Soxylat A 25-7, hexadecanol Soxylat A 25-7, polyoxyethylene octadecanol, C 12 ~ 14Alcohol mixture Soxylat A 25-7 or C 16 ~ 18The alcohol mixture Soxylat A 25-7; The number of oxyethyl group is 2~12 in the described fatty alcohol-polyoxyethylene ether.
Described sulfonated reagent is Sodium Pyrosulfite, sodium sulphite anhydrous 99.3 or sodium bisulfite.
Described sulphiting vegetables oil is sulphiting Viscotrol C, sulphiting Oleum Gossypii semen or sulphiting rapeseed oil.
The succinic acid sulphonated fat-liquoring agent that adopts succsinic acid alpha-sulfonated fatty polyoxyethylenated alcohol and sulphiting vegetables oil to prepare possesses the good emulsifying ability, good emulsion stability, and 1: 9 water miscible liquid 24 hours is not stratified.Because fatty alcohol-polyoxyethylene ether itself possesses the good emulsifying effect, after the succsinic acid sulfonation, make fatty alcohol-polyoxyethylene ether with carboxyl and sulfonic group, thereby make it possess better uniformly penetrating and with amino, hydroxyl and metal ion in the leather fiber good bonding properties is arranged, make the fatting agent in the finished leather be difficult for wash-out, migration.After using this fatting agent that leather is carried out stuffing and processes, leather not only has good flexibility, homogeneity and fullness, and possesses good springiness, the good and advantage such as low haze value of fast light resistance toheat.
Embodiment
Below in conjunction with embodiment the present invention is described in detail.
Embodiment 1
The purification of fatty alcohol-polyoxyethylene ether: at first Dodecyl Polyoxyethylene Ether is added in the reactor, open and stir, open vacuum pump, keep vacuum tightness to be-0.1Mpa, be warming up to 100 ℃, approximately after 2 hours, lower the temperature for subsequent use.
Sulfonation reaction: in through the Dodecyl Polyoxyethylene Ether that purifies, add maleic anhydride by 1: 0.6 mol ratio, be warming up to 100 ℃, reacted 3 hours, then in reaction mass, add sodium sulphite anhydrous 99.3, the mol ratio of control sodium sulphite anhydrous 99.3 and maleic anhydride is 0.6: 1, the control temperature of reaction is 70 ℃, reacts 2 hours, obtains succsinic acid sulfonation Dodecyl Polyoxyethylene Ether.
Composite: that above-mentioned gained succsinic acid sulfonation Dodecyl Polyoxyethylene Ether is cooled to 60 ℃, add the sulphiting rapeseed oil, in the quality percentage, controlling respectively succsinic acid sulfonation Dodecyl Polyoxyethylene Ether is 70%, the sulphiting rapeseed oil is 30%, then regulates material to pH8.0 with sodium hydroxide, and it is 70% that water is adjusted to working substance content, continue to stir 1 hour, obtain succsinic acid sulfonation Dodecyl Polyoxyethylene Ether fatting agent.
Embodiment 2
The purification of fatty alcohol-polyoxyethylene ether: at first the tetradecyl alcohol Soxylat A 25-7 is added in the reactor, open and stir, open vacuum pump, keep vacuum tightness to be-0.08Mpa, be warming up to 110 ℃, approximately after 1 hour, lower the temperature for subsequent use.
Sulfonation reaction: in through the tetradecyl alcohol Soxylat A 25-7 that purifies, add maleic anhydride by 1: 1.2 mol ratio, be warming up to 120 ℃, reacted 2 hours, then in reaction mass, add Sodium Pyrosulfite, the mol ratio of control Sodium Pyrosulfite and maleic anhydride is 0.8: 1, the control temperature of reaction is 90 ℃, reacts 1.5 hours, obtains succsinic acid sulfonation tetradecyl alcohol Soxylat A 25-7.
Composite: that above-mentioned gained succsinic acid sulfonation tetradecyl alcohol Soxylat A 25-7 is cooled to 70 ℃, add the sulphiting Viscotrol C, in the quality percentage, controlling respectively succsinic acid sulfonation tetradecyl alcohol Soxylat A 25-7 is 80%, the sulphiting Viscotrol C is 20%, then regulates material to pH6.0 with sodium hydroxide, and it is 60% that water is adjusted to working substance content, continue to stir 0.7 hour, obtain succsinic acid sulfonation tetradecyl alcohol Soxylat A 25-7 fatting agent.
Embodiment 3
The purification of fatty alcohol-polyoxyethylene ether: at first the hexadecanol Soxylat A 25-7 is added in the reactor, open and stir, open vacuum pump, keep vacuum tightness to be-0.09Mpa, be warming up to 130 ℃, approximately after 0.8 hour, lower the temperature for subsequent use.
Sulfonation reaction: in through the hexadecanol Soxylat A 25-7 that purifies, add maleic anhydride by 1: 1.5 mol ratio, be warming up to 90 ℃, reacted 6 hours, then in reaction mass, add sodium bisulfite, the mol ratio of control sodium bisulfite and maleic anhydride is 1: 1, the control temperature of reaction is 100 ℃, reacts 5 hours, obtains succsinic acid sulfonation hexadecanol Soxylat A 25-7.
Composite: that above-mentioned gained succsinic acid sulfonation hexadecanol Soxylat A 25-7 is cooled to 50 ℃, add the sulphiting Oleum Gossypii semen, in the quality percentage, controlling respectively succsinic acid sulfonation hexadecanol Soxylat A 25-7 is 40%, the sulphiting Oleum Gossypii semen is 60%, then regulates material to pH7.0 with sodium hydroxide, and it is 50% that water is adjusted to working substance content, continue to stir 0.6 hour, obtain succsinic acid sulfonation hexadecanol Soxylat A 25-7 fatting agent.
Embodiment 4
The purification of fatty alcohol-polyoxyethylene ether: at first polyoxyethylene octadecanol is added in the reactor, open and stir, open vacuum pump, keep vacuum tightness to be-0.05Mpa, be warming up to 180 ℃, approximately after 1 hour, lower the temperature for subsequent use.
Sulfonation reaction: in through the polyoxyethylene octadecanol that purifies, add maleic anhydride by 1: 2 mol ratio, be warming up to 120 ℃, reacted 8 hours, then in reaction mass, add Sodium Pyrosulfite, the mol ratio of control Sodium Pyrosulfite and maleic anhydride is 0.7: 1, the control temperature of reaction is 70 ℃, reacts 2 hours, obtains succsinic acid sulfonation polyoxyethylene octadecanol.
Composite: that above-mentioned gained succsinic acid sulfonation polyoxyethylene octadecanol is cooled to 60 ℃, add the sulphiting Viscotrol C, in the quality percentage, controlling respectively succsinic acid sulfonation polyoxyethylene octadecanol is 60%, the sulphiting Viscotrol C is 40%, then regulates material to pH6.5 with sodium hydroxide, and it is 40% that water is adjusted to working substance content, continue to stir 0.8 hour, obtain succsinic acid sulfonation polyoxyethylene octadecanol fatting agent.
Embodiment 5
The purification of fatty alcohol-polyoxyethylene ether: at first with C 12-14Polyoxyethylenated alcohol adds in the reactor, opens and stirs, and opens vacuum pump, keeps vacuum tightness to be-0.03Mpa, is warming up to 100 ℃, approximately after 2 hours, lowers the temperature for subsequent use.
Sulfonation reaction: at the C through purifying 12-14Add maleic anhydride by 1: 1.2 mol ratio in the polyoxyethylenated alcohol, be warming up to 70 ℃, reacted 8 hours, then add sodium bisulfite in reaction mass, the mol ratio of control sodium bisulfite and maleic anhydride is 0.5: 1, and the control temperature of reaction is 70 ℃, reacted 4 hours, and obtained succsinic acid sulfonation C 12-14Polyoxyethylenated alcohol.
Composite: with above-mentioned gained succsinic acid sulfonation C 12-14Polyoxyethylenated alcohol is cooled to 50 ℃, adds the sulphiting rapeseed oil, in the quality percentage, controls respectively succsinic acid sulfonation C 12-14Polyoxyethylenated alcohol is 50%, and the sulphiting rapeseed oil is 50%, then regulates material to pH7.5 with sodium hydroxide, and it is 60% that water is adjusted to working substance content, continues to stir 0.7 hour, obtains succsinic acid sulfonation C 12-14The polyoxyethylenated alcohol fatting agent.
Embodiment 6
The purification of fatty alcohol-polyoxyethylene ether: at first with C 16-18Polyoxyethylenated alcohol adds in the reactor, opens and stirs, and opens vacuum pump, keeps vacuum tightness to be-0.07Mpa, is warming up to 130 ℃, approximately after 1.5 hours, lowers the temperature for subsequent use.
Sulfonation reaction: at the C through purifying 16-18Add maleic anhydride by 1: 1.6 mol ratio in the polyoxyethylenated alcohol, be warming up to 80 ℃, reacted 5 hours, then add S-WAT in reaction mass, the mol ratio of control S-WAT and maleic anhydride is 0.9: 1, and the control temperature of reaction is 90 ℃, reacted 1 hour, and obtained succsinic acid sulfonation C 16-18Polyoxyethylenated alcohol.
Composite: with above-mentioned gained succsinic acid sulfonation C 16-18Polyoxyethylenated alcohol is cooled to 70 ℃, adds the sulphiting Oleum Gossypii semen, in the quality percentage, controls respectively succsinic acid sulfonation C 16-18Polyoxyethylenated alcohol is 65%, and the sulphiting Oleum Gossypii semen is 35%, then regulates material to pH8.0 with sodium hydroxide, and it is 55% that water is adjusted to working substance content, continues to stir 0.5 hour, obtains succsinic acid sulfonation C 16-18The polyoxyethylenated alcohol fatting agent.

Claims (1)

1. the preparation method of a succinic acid sulphonated fat-liquoring agent, described succinic acid sulphonated fat-liquoring agent is by following substances and water is composite forms, in the quality percentage, succsinic acid alpha-sulfonated fatty polyoxyethylenated alcohol 30%~80%, sulphiting vegetables oil 20%~70%; It is characterized in that, comprise the steps:
⑴ the preparation of succsinic acid alpha-sulfonated fatty polyoxyethylenated alcohol:
The purification of fatty alcohol-polyoxyethylene ether: at first fatty alcohol-polyoxyethylene ether is added in the reactor, open to stir, open vacuum pump, keep vacuum tightness be-0.03MPa~-0.1MPa, be warming up to 100 ℃~180 ℃, be incubated after 0.5~2 hour, lower the temperature for subsequent use;
Sulfonation reaction: in through the fatty alcohol-polyoxyethylene ether that purifies, add maleic anhydride by 1: 0.5~2 mol ratios, be warming up to 60 ℃~130 ℃, reacted 1~8 hour; Then add sulfonated reagent in reaction mass, the mol ratio of control sulfonated reagent and maleic anhydride is 0.5~1: 1, and the control temperature of reaction is 70 ℃~100 ℃, reacts 1~5 hour, obtains succsinic acid alpha-sulfonated fatty polyoxyethylenated alcohol;
⑵ composite: step ⑴ gained succsinic acid alpha-sulfonated fatty polyoxyethylenated alcohol is cooled to 50 ℃~70 ℃, add the sulphiting vegetables oil, in the quality percentage, controlling respectively succsinic acid sulfonation Soxylat A 25-7 is 30%~80%, and the sulphiting vegetables oil is 20%~70%; Then regulate material to pH6.0~8.0 with sodium hydroxide, and water to be adjusted to working substance content be 40%~70%, continue to stir 0.5~1 hour, obtain succinic acid sulphonated fat-liquoring agent;
Described fatty alcohol-polyoxyethylene ether is Dodecyl Polyoxyethylene Ether, tetradecyl alcohol Soxylat A 25-7, hexadecanol Soxylat A 25-7, polyoxyethylene octadecanol, C 12 ~ 14Alcohol mixture Soxylat A 25-7 or C 16 ~ 18The alcohol mixture Soxylat A 25-7; The number of oxyethyl group is 2~12 in the described fatty alcohol-polyoxyethylene ether; Described sulfonated reagent is Sodium Pyrosulfite, sodium sulphite anhydrous 99.3 or sodium bisulfite; Described sulphiting vegetables oil is sulphiting Viscotrol C, sulphiting Oleum Gossypii semen or sulphiting rapeseed oil.
CN 201010503072 2010-10-12 2010-10-12 Method for preparing succinic acid sulphonated fat-liquoring agent Active CN101956030B (en)

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CN102628089B (en) * 2012-03-31 2013-08-07 陕西科技大学 Preparation method for graphene oxide-modified sulfited fatliquor
CN103088169B (en) * 2013-02-07 2014-10-22 浙江传化股份有限公司 Leather comprehensive fat liquor and preparation method of the same
CN103804678A (en) * 2014-02-08 2014-05-21 上海金兆节能科技有限公司 Fatty acid polyoxyethylene succinate and preparation method thereof and micro cutting solution prepared from fatty acid polyoxyethylene succinate
CN104804120B (en) * 2015-05-12 2017-11-07 四川德赛尔化工实业有限公司 A kind of preparation method of the polymer fatliquoring agent containing sulfosuccinates salt structure
CN105441603B (en) * 2015-11-17 2018-02-13 佛山市顺德区粤亭新材料有限公司 A kind of synthetic fat liquor and preparation method thereof
CN105778077A (en) * 2016-05-25 2016-07-20 安徽中恩化工有限公司 Preparation method of acid-alkali-resistant wetting agent
CN107794318B (en) * 2017-11-27 2020-07-10 上海金狮化工有限公司 Fur fatting agent, formula and preparation method thereof
CN110129490B (en) * 2019-05-23 2021-05-25 陕西科技大学 Preparation method of modified montmorillonite pepper seed oil flame-retardant leather greasing agent

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