CN104232811A - Method for preparing Gemini surfactant modified montmorillonite phosphorylated rapeseed oil flame-retardant fatting agent - Google Patents

Method for preparing Gemini surfactant modified montmorillonite phosphorylated rapeseed oil flame-retardant fatting agent Download PDF

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CN104232811A
CN104232811A CN201410477211.4A CN201410477211A CN104232811A CN 104232811 A CN104232811 A CN 104232811A CN 201410477211 A CN201410477211 A CN 201410477211A CN 104232811 A CN104232811 A CN 104232811A
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rapeseed oil
weight parts
gemini
add
necked flask
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CN104232811B (en
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吕斌
王泓棣
马建中
高建静
高党鸽
毛宇
张绍华
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Shandong Li Ning science and technology novel material company limited
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Shaanxi University of Science and Technology
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  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
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Abstract

The invention relates to a method for preparing a Gemini surfactant modified montmorillonite phosphorylated rapeseed oil flame-retardant fatting agent. The method comprises the steps as follows: rapeseed oil is dried by anhydrous calcium chloride through decompression dehydration, methyl alcohol and a catalyst NaOH are added and react at the temperature of 60-70 DEG C for 2 hours, and rapeseed oil methyl ester is obtained through separation and purification; rapeseed oil methyl ester and P2O5 dispersed by 5# white oil are blended at the temperature of 0 DEG C, the temperature is increased to 70 DEG C, the reaction is performed for 4.5 hours, pH is regulated to 7.5, reaction is performed for 30 min, and phosphorylated rapeseed oil is obtained after cooling; Na-montmorillonite is dispersed in water, serial Gemini surfactant is added, the reaction is performed at the temperature of 90 DEG C for 4 hours, and the Gemini surfactant modified montmorillonite is obtained; and the phosphorylated rapeseed oil and the modified montmorillonite are added in a three-neck flask, stirred at the temperature of 40 DEG C for 20 min and subjected to ultrasonography for 30 min, so that the Gemini surfactant modified montmorillonite phosphorylated compound fatting agent is prepared. Interlayer spacing of montmorillonite modified by the Gemini surfactant is increased, and accordingly, flame-retardant performance and mechanical performance of leather after fat liquoring are improved.

Description

The preparation method of the fire-retardant fatting agent of Gemini surface active modified montmorillonoid phosphorylation rapeseed oil
Technical field
The present invention relates to a kind of preparation method of leather rapeseed oil fatting agent, be specifically related to the preparation method of the fire-retardant fatting agent of a kind of Gemini surface active modified montmorillonoid phosphorylation rapeseed oil.
Background technology
Fatting agent is a kind of important leather chemicals in leather processing procedure.Leather produce in stuffing be under certain processing condition, process leather with grease or fatting agent, make leather absorb a certain amount of grease and give leather plentiful, soft, there is the characteristics such as elasticity.Fatting agent, while giving the good properties of leather, because the combination between its with leather fiber is firmly lower, very easily migrates to leather surface, directly becomes combustion source, thus improve the inflammableness of leather in heat-processed.Therefore, flame retardant resistance has become one of requirement of manufacture leather.
Containing phosphate radical isoreactivity group in the molecule of phosphorylation fatting agent, there is the ability of stronger acidproof, alkaline-resisting, salt tolerant, can with the chromium complexing in leather fiber, leather after stuffing is soft, plentiful, there is certain select operator and flame retardant resistance, the position that can reduce hide is poor, improves the water resistance of leather, has permanent stuffing effect.The unique texture of the two hydrophobic group of double-hydrophilic of Gemini surface active, has the character such as wettability, emulsifying property, dispersiveness and the lyotropy being better than conventional surfactant.Adopt it to carry out modification to polynite, effectively can increase the interlamellar spacing of polynite, make polynite lipophilicity stronger, better performance nano effect, better disperse in organic matrix, be conducive to polynite being introduced in phosphorylation rapeseed oil, improve flame retardant properties and the mechanical property of leather further.
The flame retardant properties of fatting agent in the market and mechanical property can not meet the demand of people, and needing provides a kind of flame retardant properties better fatting agent.
Summary of the invention
The object of the invention is to the flame retardant properties improving leather, provide the preparation method of the fire-retardant fatting agent of a kind of Gemini surface active modified montmorillonoid phosphorylation rapeseed oil.
For achieving the above object, the technical solution used in the present invention is:
The preparation method of the fire-retardant fatting agent of Gemini surface active modified montmorillonoid phosphorylation rapeseed oil, is characterized in that:
Comprise the following steps:
Step one: the preparation of phosphorylation rapeseed oil:
The rapeseed oil Calcium Chloride Powder Anhydrous of 40 weight parts is carried out drying, decompression dehydration simultaneously, add the methyl alcohol of 120 weight parts, put into there-necked flask, then add the solid NaOH catalyzer of 1.2 weight parts, temperature of reaction controls at 60 DEG C ~ 70 DEG C, stirring and refluxing 2h, after reaction terminates, carry out air distillation, reclaim excessive alcohol; Reclaim catalyzer with filtered on buchner funnel, filtrate puts into pear shape separatory funnel stratification, and upper strata is rapeseed methylester;
In there-necked flask, add the gained rapeseed methylester of 50 weight parts taken, the P of 58 ~ 67.5 weight parts 2o 5, by the 5# white oil of 116 ~ 135 weight parts dispersion P 2o 5add in there-necked flask, add in ice-water bath, at the temperature of 70 DEG C, react 4.5h, regulate about pH to 7.5, continue reaction 30min, be cooled to room temperature and pour out product phosphorylation rapeseed oil;
Step 2: the preparation of Gemini cats product modified montmorillonoid:
The water getting 100 weight parts adds in there-necked flask, more slowly adds the sodium-based montmorillonite of 10 weight parts, stirs 30min; In there-necked flask, add the Gemini type cats product of the different chain length of 6.275 ~ 7.064 weight parts respectively, be warming up to 90 DEG C, isothermal reaction 4h, Chun Xi ﹑ washed several times with water, 100 DEG C ~ 120 DEG C dry 24h; Grinding, obtains Gemini type cats product modified montmorillonoid;
Step 3: the preparation of Gemini surface active modified montmorillonoid fat liquoring complex agent:
Get 50 parts by weight of phosphoric acid rapeseed oils adds in there-necked flask together with the Gemini cats product modified montmorillonoid of 1 ~ 5 weight part, be warming up to 40 DEG C, temperature control reaction 20min, supersound process 30min, obtained Gemini cats product modified montmorillonoid phosphorylation rapeseed oil flame retardant type fatting agent.
In step 2, the Gemini type cats product of different chain length is selected from trimethylene base [(lauramide propyl-dimethyl/palmitamide propyl-dimethyl) ammonium chloride], trimethylene base [(myristamide propyl-dimethyl/palmitamide propyl-dimethyl) ammonium chloride], trimethylene base two [(lauramide propyl-dimethyl) ammonium chloride], trimethylene base two [(palmitamide propyl-dimethyl) ammonium chloride].
The invention has the advantages that: in this fatting agent, introduce ignition-proof element phosphorus and modified montmorillonoid, to reach the object improving Leather Flame Retardant after stuffing.Select rapeseed oil cheap and easy to get to be grease matrix, introduce phosphate by phosphorylation modification, make fatting agent self have certain flame retardant properties.Then in phosphorylation rapeseed oil, polynite and cats product is introduced, prepare nano combined fatting agent, the N in the quaternary ammonium cation in the Gemini type cats product selected and the P in phosphorylation forms the effect that cooperative flame retardant is played in a N-P Intumescent Retardant System and polynite jointly.Present method is relatively simple, and the cheating engaging layer spacing using Gemini surface active modified increases, and is conducive to the performance of its nano effect, also further increases polynite dispersion stabilization in the composite and homogeneity.The Gemini type cats product modified montmorillonoid phosphorylation rapeseed oil fire-retardant fatting agent grain side of leather of preparation is careful, except there is traditional fatliquoring function, there is good flame retardant properties and mechanical property, flexibility and fullness well, are a kind of leather function fatting agents of excellent property.
embodiment:
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1:
(1) the rape oil Calcium Chloride Powder Anhydrous of 40 weight parts is carried out drying, decompression dehydration simultaneously, add the methyl alcohol of 120 weight parts, put into there-necked flask, then add the solid NaOH catalyzer of 1.2 weight parts, temperature of reaction controls at 65 DEG C of stirring and refluxing 2h, after reaction terminates, carry out air distillation, reclaim excessive alcohol; Reclaim catalyzer with filtered on buchner funnel, filtrate puts into pear shape separatory funnel stratification, and upper strata is rapeseed methylester.In there-necked flask, add the gained rapeseed methylester of 50 weight parts taken, the P of 60 weight parts 2o 5, with the 5# white oil dispersion P of 120 weight parts 2o 5add in there-necked flask, add in ice-water bath, at the temperature of 70 DEG C, react 4.5h, regulate pH to 7.5, continue reaction 30min, regulate solid content to be 40%, be cooled to room temperature and pour out product, obtain phosphorylation rapeseed oil.
(2) in there-necked flask, add the water of 100 weight parts, slowly add the sodium-based montmorillonite of 10 weight parts, stir 30min; The trimethylene base [(lauramide propyl-dimethyl/palmitamide propyl-dimethyl) ammonium chloride] of 6.8 weight parts is added respectively in there-necked flask, be warming up to 90 DEG C, isothermal reaction 4h Chun Xi ﹑ washed several times with water, 110 DEG C of dry 24h, grinding, obtain Gemini type cats product modified montmorillonoid.
(3) get 50 parts by weight of phosphoric acid rapeseed oils adds in there-necked flask together with the modified montmorillonoid of 5 weight parts, be warming up to 40 DEG C, temperature control reaction 20min, supersound process 30min, obtained Gemini cats product modified montmorillonoid phosphorylation rapeseed oil flame retardant type fatting agent.
Embodiment 2:
(1) the rape oil Calcium Chloride Powder Anhydrous of 40 weight parts is carried out drying, decompression dehydration simultaneously, add the methyl alcohol of 120 weight parts, put into there-necked flask, then add the solid NaOH catalyzer of 1.2 weight parts, temperature of reaction controls at 70 DEG C of stirring and refluxing 2h, after reaction terminates, carry out air distillation, reclaim excessive alcohol; Reclaim catalyzer with filtered on buchner funnel, filtrate puts into pear shape separatory funnel stratification, and upper strata is rapeseed methylester.In there-necked flask, add the gained rapeseed methylester of 50 weight parts taken, the P of 62 weight parts 2o 5, with the 5# white oil dispersion P of 124 weight parts 2o 5add in there-necked flask, add in ice-water bath, at the temperature of 70 DEG C, react 4.5h, regulate pH to 7.5, continue reaction 30min, be cooled to room temperature and pour out product, obtain phosphorylation rapeseed oil.
(2) in there-necked flask, add the water of 100 weight parts, slowly add the sodium-based montmorillonite of 10 weight parts, stir 30min; The trimethylene base [(myristamide propyl-dimethyl/palmitamide propyl-dimethyl) ammonium chloride] of 7.064 weight parts is added respectively in there-necked flask, be warming up to 90 DEG C, isothermal reaction 4h Chun Xi ﹑ washed several times with water, 120 DEG C of dry 24h, grinding, obtain Gemini type cats product modified montmorillonoid.
(3) modified montmorillonoid getting 50 parts by weight of phosphoric acid rapeseed oil 3 weight parts adds in there-necked flask together, be warming up to 40 DEG C, temperature control reaction 20min, supersound process 30min, obtained Gemini cats product modified montmorillonoid phosphorylation rapeseed oil flame retardant type fatting agent.
Embodiment 3:
(1) the rape oil Calcium Chloride Powder Anhydrous of 40 weight parts is carried out drying, decompression dehydration simultaneously, add the methyl alcohol of 120 weight parts, put into there-necked flask, then add the solid NaOH catalyzer of 1.2 weight parts, temperature of reaction controls at 67 DEG C of stirring and refluxing 2h, after reaction terminates, carry out air distillation, reclaim excessive alcohol; Reclaim catalyzer with filtered on buchner funnel, filtrate puts into pear shape separatory funnel stratification, and upper strata is rapeseed methylester.In there-necked flask, add the gained rapeseed methylester of 50 weight parts taken, the P of 67 weight parts 2o 5, with the 5# white oil dispersion P of 134 weight parts 2o 5add in there-necked flask, add in ice-water bath, at the temperature of 70 DEG C, react 4.5h, regulate pH to 7.5, continue reaction 30min, be cooled to room temperature and pour out product, obtain phosphorylation rapeseed oil.
(2) in there-necked flask, add the water of 100 weight parts, slowly add the sodium-based montmorillonite of 10 weight parts, stir 30min; In there-necked flask, add the trimethylene base two [(lauramide propyl-dimethyl) ammonium chloride] of 6.28 weight parts respectively, be warming up to 90 DEG C, isothermal reaction 4h Chun Xi ﹑ washed several times with water, 115 DEG C of dry 24h, grinding, obtains Gemini type cats product modified montmorillonoid.
(3) get 50 parts by weight of phosphoric acid rapeseed oils adds in there-necked flask together with the modified montmorillonoid of 1 weight part, be warming up to 40 DEG C, temperature control reaction 20min, supersound process 30min, obtained Gemini cats product modified montmorillonoid phosphorylation rapeseed oil flame retardant type fatting agent.
Embodiment 4:
(1) the rape oil Calcium Chloride Powder Anhydrous of 40 weight parts is carried out drying, decompression dehydration simultaneously, add the methyl alcohol of 120 weight parts, put into there-necked flask, then add the solid NaOH catalyzer of 1.2 weight parts, temperature of reaction controls at 68 DEG C of stirring and refluxing 2h, after reaction terminates, carry out air distillation, reclaim excessive alcohol; Reclaim catalyzer with filtered on buchner funnel, filtrate puts into pear shape separatory funnel stratification, and upper strata is rapeseed methylester.In there-necked flask, add the gained rapeseed methylester of 50 weight parts taken, the P of 59 weight parts 2o 5, with the 5# white oil dispersion P of 118 weight parts 2o 5add in there-necked flask, add in ice-water bath, at the temperature of 70 DEG C, react 4.5h, regulate pH to 7.5, continue reaction 30min, be cooled to room temperature and pour out product, obtain phosphorylation rapeseed oil.
(2) in there-necked flask, add the water of 100 weight parts, slowly add the sodium-based montmorillonite of 10 weight parts, stir 30min; The trimethylene base two [(palmitamide propyl-dimethyl) ammonium chloride] of 6.8 weight parts is added respectively in there-necked flask, be warming up to 90 DEG C, isothermal reaction 4h, Chun Xi ﹑ washed several times with water, 100 DEG C of dry 24h, grinding, obtain Gemini type cats product modified montmorillonoid.
(3) 50 parts by weight of phosphoric acid rapeseed oils add in there-necked flask together with the modified montmorillonoid of 2.5 weight parts, be warming up to 40 DEG C, temperature control reaction 20min, supersound process 30min, obtained Gemini cats product modified montmorillonoid phosphorylation rapeseed oil flame retardant type fatting agent.
The performance test results of Gemini surface active modified montmorillonoid phosphorylation rapeseed oil fatting agent sees the following form:
Note: No. 1 sample for not add Gemini cats product modified montmorillonoid, leather after modified colza fatting agent stuffing obtained by the same way; No. 2 samples are for obtaining leather after the stuffing of Gemini cats product modified montmorillonoid phosphorylation rapeseed oil fatting agent according to present method.
Can find out, after obtained Gemini cats product modified montmorillonoid phosphorylation rapeseed oil flame retardant type fatting agent stuffing, grain side of leather is careful, and have good flame retardant properties, mechanical property significantly improves, and fullness is good.

Claims (2)

  1. The preparation method of the fire-retardant fatting agent of 1.Gemini surfactant-modified polynite phosphorylation rapeseed oil, is characterized in that:
    Comprise the following steps:
    Step one: the preparation of phosphorylation rapeseed oil:
    The rapeseed oil Calcium Chloride Powder Anhydrous of 40 weight parts is carried out drying, decompression dehydration simultaneously, add the methyl alcohol of 120 weight parts, put into there-necked flask, then add the solid NaOH catalyzer of 1.2 weight parts, temperature of reaction controls at 60 DEG C ~ 70 DEG C, stirring and refluxing 2h, after reaction terminates, carry out air distillation, reclaim excessive alcohol; Reclaim catalyzer with filtered on buchner funnel, filtrate puts into pear shape separatory funnel stratification, and upper strata is rapeseed methylester;
    In there-necked flask, add the gained rapeseed methylester of 50 weight parts taken, the P of 58 ~ 67.5 weight parts 2o 5, by the 5# white oil of 116 ~ 135 weight parts dispersion P 2o 5add in there-necked flask, add in ice-water bath, at the temperature of 70 DEG C, react 4.5h, regulate about pH to 7.5, continue reaction 30min, be cooled to room temperature and pour out product phosphorylation rapeseed oil;
    Step 2: the preparation of Gemini cats product modified montmorillonoid:
    The water getting 100 weight parts adds in there-necked flask, more slowly adds the sodium-based montmorillonite of 10 weight parts, stirs 30min; In there-necked flask, add the Gemini type cats product of the different chain length of 6.275 ~ 7.064 weight parts respectively, be warming up to 90 DEG C, isothermal reaction 4h, Chun Xi ﹑ washed several times with water, 100 DEG C ~ 120 DEG C dry 24h; Grinding, obtains Gemini type cats product modified montmorillonoid;
    Step 3: the preparation of Gemini surface active modified montmorillonoid fat liquoring complex agent:
    Get 50 parts by weight of phosphoric acid rapeseed oils adds in there-necked flask together with the Gemini cats product modified montmorillonoid of 1 ~ 5 weight part, be warming up to 40 DEG C, temperature control reaction 20min, supersound process 30min, obtained Gemini cats product modified montmorillonoid phosphorylation rapeseed oil flame retardant type fatting agent.
  2. 2. the preparation method of the fire-retardant fatting agent of Gemini surface active modified montmorillonoid phosphorylation rapeseed oil according to claim 1, is characterized in that:
    In step 2, the Gemini type cats product of different chain length is selected from trimethylene base [(lauramide propyl-dimethyl/palmitamide propyl-dimethyl) ammonium chloride], trimethylene base [(myristamide propyl-dimethyl/palmitamide propyl-dimethyl) ammonium chloride], trimethylene base two [(lauramide propyl-dimethyl) ammonium chloride], trimethylene base two [(palmitamide propyl-dimethyl) ammonium chloride].
CN201410477211.4A 2014-09-18 2014-09-18 The preparation method of the Gemini surface active modified montmorillonoid fire-retardant fatting agent of phosphorylation Oleum Brassicae campestris Active CN104232811B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108654703A (en) * 2017-03-31 2018-10-16 南京理工大学 A kind of preparation method of Gemini surface active agent pillared modification montmorillonite

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR940007335B1 (en) * 1991-11-26 1994-08-13 주식회사 럭키 Fat liquoring-compositions of leather
CN101633965A (en) * 2009-08-20 2010-01-27 陕西科技大学 Flame-retardant polymer/montmorillonite nano fat liquoring complex agent
CN102617864A (en) * 2012-03-31 2012-08-01 陕西科技大学 Phosphate leather fat liquoring agent and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR940007335B1 (en) * 1991-11-26 1994-08-13 주식회사 럭키 Fat liquoring-compositions of leather
CN101633965A (en) * 2009-08-20 2010-01-27 陕西科技大学 Flame-retardant polymer/montmorillonite nano fat liquoring complex agent
CN102617864A (en) * 2012-03-31 2012-08-01 陕西科技大学 Phosphate leather fat liquoring agent and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108654703A (en) * 2017-03-31 2018-10-16 南京理工大学 A kind of preparation method of Gemini surface active agent pillared modification montmorillonite

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