CN101736581A - Hydrophilic softening agent and preparing method thereof - Google Patents
Hydrophilic softening agent and preparing method thereof Download PDFInfo
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- CN101736581A CN101736581A CN200910264412A CN200910264412A CN101736581A CN 101736581 A CN101736581 A CN 101736581A CN 200910264412 A CN200910264412 A CN 200910264412A CN 200910264412 A CN200910264412 A CN 200910264412A CN 101736581 A CN101736581 A CN 101736581A
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- softening agent
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- hydrophilic softening
- hydrophilic
- diethylenetriamine
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Abstract
The invention discloses a hydrophilic softening agent and a preparing method thereof. The hydrophilic softening agent contains 70%-90% of quaternary softening agent active matter, and 10%-30% of anhydrous low-carbon solvent with low boiling point or anhydrous water-soluble solvent with high boiling point. The softening agent is free from phosphorus and the harmful substances of alkylphenol ethoxylates, formaldehyde and the like, can be biologically degraded, has the soft, hydrophilic and anti-static functions, and is used for the after treatment of cellulose fiber and the softening arrangement of papermaking, leather and the like.
Description
Technical field
The present invention relates to hydrophilic softening agent that in textile dyeing and finishing, papermaking and leather industry, uses and preparation method thereof.
Background technology
The softener that uses in the weaving generally can be divided into silicone based and the non-organic silicon class, and the latter mainly is the product of cation type, generally with saturated 16, stearic acid, with reactions such as AEEA, diethylenetriamines, obtain imidazoline or acid amides, obtain mill run in quaternized, acidifying.This series products soft effect is pretty good, but not hydrophilic.The softener of good hydrophilic property can have antistatic, moistening effect in softness, comfortable and easy to wear.
Unsaturated acids is replaced saturated acid, according to above-mentioned technology, can obtain corresponding hydrophilic softener, the title of this series products ointment or consistent lubricant on market is being sold.But this series products often increases AEEA in order to reach hydrophily preferably, the ratio of diethylenetriamine, and unhindered amina in the product (primary amine, secondary amine) is many, uses the easy xanthochromia of back fabric.
The patent No. is the patent of CN97182299.9, discloses a kind of production method of quaternary fatty acid triethanolamine salt softener, and the advantage of this softener is that xanthochromia is little, and maximum shortcoming is not alkaline-resisting, non-refractory.
External STEPAN company, there has been this series products in EVONIK company, ACCOSOFT550-75 for example, VARISOFT 222SB etc., but do not point out the molal quantity of oxirane addition; Domestic not appearing in the newspapers do not seen product introduction yet.Because this series products will be used dangerous, hypertoxic chemicals such as oxirane, dimethyl suflfate, general factory is difficult to possess simultaneously above-mentioned raw materials; In addition, in the production equipment, personnel, technology are required also very high, thereby, domestic this series products few people research, produce.
Summary of the invention
First goal of the invention of the present invention is to be to overcome the deficiencies in the prior art part, and a kind of good hydrophilic property is provided, easily degraded and the difficult hydrophilic softening agent that xanthochromia takes place.
Second goal of the invention of the present invention is to provide a kind of rational practicable preparation method for above-mentioned hydrophilic softening agent.
First goal of the invention of the present invention is achieved through the following technical solutions: a kind of hydrophilic softening agent, the percentage by weight of its constituent is: quaternary ammonium salt softener active matter 70%～90%, anhydrous low boiling low-carbon alcohols solvent or anhydrous higher boiling water-soluble alcohol solvent 10%～30%.
Wherein above-mentioned solvent can be anhydrous low boiling low-carbon alcohols or anhydrous higher boiling water-soluble alcohol separately or/mix use with any proportioning, anhydrous low boiling low-carbon alcohols can be ethanol, normal propyl alcohol, isopropyl alcohol, can be that this three mixing independent or any proportioning is used, anhydrous higher boiling water-soluble alcohol can be ethylene glycol, propylene glycol, can be the use of the independent or any proportioning of the two.
A kind of preparation method of hydrophilic softening agent is used for preparing above-mentioned hydrophilic softening agent, and its step comprises:
1) get the raw materials ready: raw material has unrighted acid, diethylenetriamine, oxirane, quaternizing agent, anhydrous low boiling low-carbon alcohols or anhydrous higher boiling water-soluble alcohol.
2) in reactor, prepare hydrophilic softening agent: add unrighted acid in the reactor, pour the nitrogen replacement secondary, under 80 ℃ temperature, begin to stir the adding diethylenetriamine, be warmed up to 160-170 ℃ gradually, be incubated 5 hours, carry out amidation process by unrighted acid and diethylenetriamine, dehydration obtains bisamide;
Cool to 100-120 ℃, in confined conditions, slowly add oxirane, carry out ethoxylation, obtain ethyoxyl bisamide base ethyl tertiary amine;
Cooling once more, and add anhydrous low boiling low-carbon alcohols or anhydrous higher boiling water-soluble alcohol and only add wherein a kind of here, the weight ratio that addition accounts for whole hydrophilic gentle right agent is 5%～10%, in the time of 60-80 ℃, drip quaternizing agent and carry out quaterisation, and 80 ℃ of insulations 3 hours, obtain quaternary ammonium salt softener active matter, quaternary ammonium salt softener active matter and solvent obtain hydrophilic softening agent in proportioning ratio proportioning.
Above-mentioned aliphatic acid is selected lighter color for use, smell is little, raw material that peroxide content is little such as oelic acid, cattle and sheep oleic acid etc., diethylenetriamine is selected purity for use to be more than 99% and not to contain the raw material of ethylenediamine, oxirane, quaternizing agent are technical grade, quaternizing agent can be dimethyl suflfate, dithyl sulfate, chloromethanes, chloroethanes etc., preferably sulfuric acid dimethyl ester, dithyl sulfate.
The chemical formula that above-mentioned unrighted acid and diethylenetriamine carry out amidation process is:
2RCOOH+H
2NCH
2CH
2NH?CH
2CH
2NH
2→RCONHCH
2CH
2NH?CH
2CH
2NHOCR
The chemical formula of above-mentioned ethoxylation is:
The chemical formula of above-mentioned quaterisation is:
The specific embodiment
Embodiment 1:
In stainless steel cauldron with conditions such as heating, cooling, nitrogen protection, stirring, temperature, pressure indication (record) and chargings; add acid number 210mgKOH/g; iodine number is greater than 100GI2/100g refined plant fatty acid oil (oleic acid) 534.3g (2.00mole); the nitrogen vacuum displacement; stir; add diethylenetriamine 103g (1.0mole) under nitrogen protection, the mol ratio of the two is 2: 1.Slowly be warmed up to 160 ℃, and be incubated 5 hours, in this process, the water generation is arranged and deviate from system, less than 3mgKOH/g, obtain yellow liquid shape amido amine intermediate to acid number.The amidation process of aliphatic acid and diethylenetriamine will dewater, moles of fatty acids dehydration is one mole in theory, generally the mol ratio of the two is about 2: 1, surpassing this ratio triamide just generates easily, its difficulty is dispersed in the water, does not have hydrophily, but also is not less than 1.8: 1.0, at this moment, bisamide is most in the product.The terminal point of reaction can represent that acid number is low more with acid number, react complete more, generally is controlled to get final product below the 3mgKOH/g.The temperature of reaction is high more, and it is fast more that acid number descends, but too high temperature can make product color deepen, and generally is controlled at 160 ℃ and get final product, reaches the reduction acid number by the reaction time, protects the purpose of color and luster.
Cool to 100 ℃, (close nitrogen and other valves) in confined conditions, 100-130 ℃ of temperature of control, pressure is less than 0.2MPa, and addition of ethylene oxide 132g, and continue insulation 30 minutes obtains the addition of ethylene oxide number and is 3 intermediate, and product is a yellow liquid.The ethoxylation ratio is easier to, and it is too fast mainly to prevent to feed in raw material, and local reaction is violent, cause product addition of ethylene oxide number unbalanced, and cause localized hyperthermia easily, color and luster deepens, influence product quality, normal reaction condition is 100-130 ℃, and pressure is not more than 0.3MPa.In the reaction later stage, should be incubated more than 30 minutes, guarantee residual oxirane complete reaction.
Nitrogen insulation continues to cool to 80 ℃, adds 5% isopropyl alcohol, 60-80 ℃ drip down dimethyl suflfate 122g (with the mol ratio of diethylenetriamine be 0.97: 1.00), be controlled at and added in 1-2 hour, and 80-83 ℃ of insulation 3-6 hour.Obtain the two oleamide base ethyl polyethoxy methylsulfuric acid ammonium methyl quaternary ammonium salts of product.The dimethyl suflfate quaterisation initial stage is very easy to reaction, needs low temperature, preferably has under the condition of solvent dilution to carry out.Solvent is generally selected the solvent of good water solubility such as absolute ethyl alcohol, propyl alcohol, isopropyl alcohol and high boiling ethylene glycol, diethylene glycol, propylene glycol, initial reaction is being carried out below 80 ℃, later stage can suitably be improved 80-90 ℃ in order to make residual dimethyl suflfate complete reaction.The addition of dimethyl suflfate can not be higher than the molar weight of tertiary amine intermediate (II), otherwise it is residual to have hypertoxic dimethyl suflfate in the product, causes accident; But can not be low excessively, influence the effect of product.Generally be controlled at dimethyl suflfate and diethylenetriamine mol ratio at 0.95-0.99: 1.0 get final product.
Add 5% isopropyl alcohol and the phosphorous acid of 1-3 ‰ or sodium thiosulfate saturated solution again.Obtain the softener product of the yellow transparent of active matter content 90%.Product can be dispersed in the normal-temperature water fast.Can add a small amount of restitutive protection's raw material in the final products, improve the color stability of product in packing, storage life.For example phosphorous acid, sodium thiosulfate etc.
Embodiment 2:
In example 1, calculate with refining tallow oil acid substitution vegetable oil, with the mol ratio of diethylenetriamine be 1.90: 1.00, the mol ratio of oxirane and diethylenetriamine is 5.0: 1.0, the mol ratio of other raw materials and diethylenetriamine is constant, and reaction condition is constant, and solvent changes 1 into, 2-propylene glycol, other conditions according to example 1 can obtain two cattle and sheep oleic acid amido-ethyl polyethoxy methylsulfuric acid ammonium methyl quaternary ammonium salts.Outward appearance is a paste, active matter content 90%.Product needed warm water disperses.
Claims (7)
1. a hydrophilic softening agent is characterized in that the percentage by weight of its constituent is: quaternary ammonium salt softener active matter 70%～90%, anhydrous low boiling low-carbon alcohols solvent or anhydrous higher boiling water-soluble alcohol solvent 10%～30%.
2. hydrophilic softening agent as claimed in claim 1.It is characterized in that described anhydrous low boiling low-carbon alcohols can be ethanol, normal propyl alcohol, isopropyl alcohol, anhydrous higher boiling water-soluble alcohol can be ethylene glycol, propylene glycol.
3. the preparation method of a hydrophilic softening agent is used for preparing the hydrophilic softening agent of telling a story in the claim 1, it is characterized in that its processing step comprises:
1) get the raw materials ready: raw material has unrighted acid, diethylenetriamine, oxirane, quaternizing agent, anhydrous low boiling low-carbon alcohols or anhydrous higher boiling water-soluble alcohol.
2) in reactor, prepare hydrophilic softening agent: add unrighted acid in the reactor, pour the nitrogen replacement secondary, under 80 ℃ temperature, begin to stir the adding diethylenetriamine, be warmed up to 160-170 ℃ gradually, be incubated 5 hours, carry out amidation process by unrighted acid and diethylenetriamine, dehydration obtains bisamide;
Cool to 100-120 ℃, in confined conditions, slowly add oxirane, carry out ethoxylation, obtain ethyoxyl bisamide base ethyl tertiary amine;
Cooling once more, and add anhydrous low boiling low-carbon alcohols or anhydrous higher boiling water-soluble alcohol, here only add wherein a kind of, the weight ratio that addition accounts for whole hydrophilic gentle right agent is 5%～10%, in the time of 60-80 ℃, drip quaternizing agent and carry out quaterisation, and, obtaining quaternary ammonium salt softener active matter 80 ℃ of insulations 3 hours, quaternary ammonium salt softener active matter and solvent obtain hydrophilic softening agent in proportioning ratio proportioning.
4. the preparation method of hydrophilic softening agent as claimed in claim 3, it is characterized in that raw material described in its step 1): aliphatic acid is selected lighter color for use, smell is little, raw material that peroxide content is little such as oelic acid, cattle and sheep oleic acid etc., diethylenetriamine is selected purity for use to be more than 99% and not to contain the raw material of ethylenediamine, oxirane, quaternizing agent are technical grade, and quaternizing agent can be dimethyl suflfate, dithyl sulfate, chloromethanes, chloroethanes etc., preferably sulfuric acid dimethyl ester, dithyl sulfate.
5. the preparation method of hydrophilic softening agent as claimed in claim 3 is characterized in that step 2) described in unrighted acid and diethylenetriamine carry out the amidation process chemical formula and be:
2RCOOH+H
2NCH
2CH
2NH?CH
2CH
2NH
2→RCONHCH
2CH
2NH?CH
2CH
2NHOCR
6. the preparation method of hydrophilic softening agent as claimed in claim 3 is characterized in that step 2) described in oxygen glycosylation reaction chemical formula be:
7. the preparation method of hydrophilic softening agent as claimed in claim 3 is characterized in that step 2) described in unrighted acid and diethylenetriamine carry out the amidation process chemical formula and be:
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| CN200910264412A CN101736581A (en) | 2009-12-22 | 2009-12-22 | Hydrophilic softening agent and preparing method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102505495A (en) * | 2011-11-10 | 2012-06-20 | 浙江传化股份有限公司 | High-elastic smooth silicon softener and preparation method and application thereof |
| CN110592939A (en) * | 2019-09-16 | 2019-12-20 | 苏州联胜化学有限公司 | Thermal yellowing resistant soft sheet and synthesis method thereof |
| CN111848945A (en) * | 2020-05-07 | 2020-10-30 | 苏州联胜化学有限公司 | Polyester fluffy hydrophilic film |
-
2009
- 2009-12-22 CN CN200910264412A patent/CN101736581A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102505495A (en) * | 2011-11-10 | 2012-06-20 | 浙江传化股份有限公司 | High-elastic smooth silicon softener and preparation method and application thereof |
| CN102505495B (en) * | 2011-11-10 | 2014-01-01 | 浙江传化股份有限公司 | High-elastic smooth silicon softener and preparation method and application thereof |
| CN110592939A (en) * | 2019-09-16 | 2019-12-20 | 苏州联胜化学有限公司 | Thermal yellowing resistant soft sheet and synthesis method thereof |
| CN111848945A (en) * | 2020-05-07 | 2020-10-30 | 苏州联胜化学有限公司 | Polyester fluffy hydrophilic film |
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Open date: 20100616 |