CN103908926A - A dimeric polyoxyethylene ether trisiloxane surfactant and a preparing method thereof - Google Patents
A dimeric polyoxyethylene ether trisiloxane surfactant and a preparing method thereof Download PDFInfo
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- CN103908926A CN103908926A CN201410097019.2A CN201410097019A CN103908926A CN 103908926 A CN103908926 A CN 103908926A CN 201410097019 A CN201410097019 A CN 201410097019A CN 103908926 A CN103908926 A CN 103908926A
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Abstract
The invention provides a dimeric polyoxyethylene ether trisiloxane surfactant. The formula of the surfactant is shown in the specification. The invention also provides a preparing method of the dimeric polyoxyethylene ether trisiloxane surfactant. The preparing method includes: subjecting allyl polyoxyethylene ether and 1,6-hexamethylene diisocyanate to a reaction under the action of a tin catalyst to obtain a product, subjecting the product and 1,1,1,3,5,5,5-heptamethyl trisiloxane to a reaction under the action of a platinum catalyst, and vacuumizing to remove solvent so as to obtain the dimeric polyoxyethylene ether trisiloxane surfactant. The dimeric polyoxyethylene ether trisiloxane surfactant is good in surface activity, capable of significantly reducing surface tension of water, and good in spreadability, and can be used as an auxiliary for pesticides or aqueous paint formulas. In addition, the preparing method of the surfactant has characteristics of mild and controllable reaction conditions, high product yield and low cost, and is suitable for large-scale industrial production.
Description
Technical field
The present invention relates to a kind of surfactant and preparation method thereof, relate in particular to a kind of organic silicon surfactant and preparation method thereof, particularly a kind of double type APEO trisiloxane surfactant and preparation method thereof.
Background technology
Surfactant is one of important industrial auxiliary agent, is described as " industrial monosodium glutamate ", has been widely applied to daily life, industrial and agricultural production and high-technology field.In many industries, surfactant plays a part crucial touch, as long as little amount can improve the physicochemical properties at material surface (interface) significantly, improvement of production process, reduces energy consumption and improves the quality of products.
Along with the reinforcement of global range environmental consciousness, the surfactant using in daily life and industrial circle is proposed to many new demands.In recent years, people are devoted to explore and synthesize the novel surfactant with high surface always.Last century Mo, novel surfactants with special construction developed in succession, and wherein one is called as double type surfactant.Gemini surface active agent is to have two or more hydrophilic radicals and more than two hydrophobic grouping, and the surfactant of new generation being connected by chemical bond by linking group.Double type surfactant molecule contains two hydrophobic chains, hydrophobicity is stronger, and connection base in double type surfactant molecule couples together two hydrophilic groups by chemical bond, weaken the repulsion between electrostatic repulsion and the hydrated sheath thereof between hydrophilic group, promote double type surfactant molecule at the absorption on aqueous solution surface and the autohemagglutination in the aqueous solution, thereby cause it to there is very high adsorption ability and aggregation formation ability, and tend to form the aggregation of lower curvature.These premium properties make it have good application potential, and commercial application prospect is wide.
Under the situation of environmental regulation increasingly stringent, the organic silicon surfactant with special performance is the up-and-coming youngster in surfactant field, because its surface tension is little, security is good and physiology inertia has been subject to people's extensive concern.Trisiloxane surfactant is the novel organic silicon surfactant of a class, can reduce the interfacial tension of oil-water interfaces; Meanwhile, can also be at low energy hydrophobic surface wetting and spreading, this ability is called " super wetability " or " super spreadability ".Because it has excellent surface property, wetting and spreading ability, be used in the fields such as coating, weaving, daily use chemicals, papermaking, oil field, agricultural chemicals.
The synthetic of double type trisiloxane surfactant can be effectively by little organic silicon surfactant surface tension, the critical micelle concentration that the character of the good and physiology inertia of security and double type surfactant are low, various self assembly form, good surface-active, excellent solubilising power combines, adopt connection base that two siliceous amphipathic structures are linked up and can reach the unexistent character of original organic silicon surfactant, higher surface and interface activity will be there is, and also likely expand the scope of application of this type of surfactant, thereby research and develop this type of surfactant tool and be of great significance.
Summary of the invention
The object of the present invention is to provide a kind of double type APEO trisiloxane surfactant and preparation method thereof, described this double type APEO trisiloxane surfactant and preparation method thereof, will be effectively by little organic silicon surfactant surface tension, the critical micelle concentration that the character of the good and physiology inertia of security and double type surfactant are low, various self assembly form, good surface-active, excellent solubilising power combines, thereby make this surfactant there is good surface-active, can reduce significantly the surface tension of water, and spreadability is good, there is good emulsification and submissive performance.Meanwhile, this preparation method's reaction condition gentleness is controlled, and products collection efficiency is high, and cost is lower, is appropriate to the scale of chemical production.
The invention provides a kind of double type APEO trisiloxane surfactant, there is following structural formula:
.
。
Wherein n=7-8.
The present invention also provides the preparation method of above-mentioned double type APEO trisiloxane surfactant, and its reaction equation (1) and (2) are as follows:
.
(1)
。
(2)
。
The preparation method of double type APEO trisiloxane surfactant of the present invention comprises the following steps: to have agitator, thermometer, condenser and nitrogen pass in the dry four-hole boiling flask of mouth, add allyl polyethenoxy ether, 1, hexamethylene-diisocyanate and dibutyl tin laurate, pass into nitrogen, be warming up to 60-100 ℃, being preferably 70-80 ℃ reacts, wherein the amount of dibutyl tin laurate is 0.3-1%, be preferably 0.5-0.8%, allyl polyethenoxy ether and 1, mole proportioning of hexamethylene-diisocyanate is 2-2.4:1, be preferably 2-2.1:1, reaction time is 3-8 hour, be preferably 4-6 hour.After having reacted, by obtained product, 1, 1, 1, 3, 5, 5, 5-heptamethyltrisiloxane, platinum catalyst and solvent add and have agitator, thermometer, condenser and nitrogen pass in the dry four-hole boiling flask of mouth, pass into nitrogen, be warming up to 60-120 ℃, being preferably 80-110 ℃ reacts, wherein the amount of platinum catalyst is 0.0008-0.002%, be preferably 0.001-0.0015%, allyl polyethenoxy ether and 1, the product and 1 of hexamethylene-diisocyanate reaction, 1, 1, 3, 5, 5, mole proportioning of 5-heptamethyltrisiloxane is 1-1.5:2, be preferably 1-1.2:2, the time of reaction is 4-10 hour, be preferably 6-8 hour, solvent is any one in toluene or isopropyl alcohol, after having reacted, decompression can obtain double type APEO trisiloxane surfactant after removing solvent.
The double type APEO trisiloxane surfactant that the present invention is prepared, its advantage be effectively by little organic silicon surfactant surface tension, security is good and the character of physiology inertia and the low critical micelle concentration of double type surfactant, various self assembly form, good surface-active, excellent solubilising power combine, thereby make this surfactant there is good surface-active, can reduce significantly the surface tension of water, and spreadability is good, there is good emulsification and submissive performance.Meanwhile, this preparation method's reaction condition gentleness is controlled, and products collection efficiency is high, and cost is lower, is appropriate to the scale of chemical production.
Accompanying drawing explanation
Fig. 1: the hydrogen nuclear magnetic resonance figure of target product double type APEO trisiloxane surfactant of the present invention.
Fig. 2: the infrared spectrogram of target product double type APEO trisiloxane surfactant of the present invention.
The specific embodiment
Below in conjunction with embodiment, the present invention is made an explanation.
Embodiment 1
.
Having in the dry four-hole boiling flask that agitator, thermometer, condenser and nitrogen passes into mouthful, add allyl polyethenoxy ether 48.66g, 1, hexamethylene-diisocyanate 9.52g and dibutyl tin laurate 0.29g, pass into nitrogen, is warming up to 70 ℃ of reactions 6 hours.After having reacted, by obtained product 58.15g, 1,1,1,3,5,5,5-heptamethyltrisiloxane 21.71g, platinum catalyst 0.34g and toluene 30mL add there is agitator, in dry four-hole boiling flask that thermometer, condenser and nitrogen pass into mouthful, pass into nitrogen, be warming up to 90 ℃ of reactions 8 hours, after having reacted, decompression can obtain double type APEO trisiloxane surfactant after removing toluene.
Embodiment 2
.
Having in the dry four-hole boiling flask that agitator, thermometer, condenser and nitrogen passes into mouthful, add allyl polyethenoxy ether 32.38g, 1, hexamethylene-diisocyanate 6.32g and dibutyl tin laurate 0.18g, pass into nitrogen, is warming up to 75 ℃ of reactions 5 o'clock.After having reacted, by obtained product 38.68g, 1,1,1,3,5,5,5-heptamethyltrisiloxane 14.53g, platinum catalyst 0.28g and toluene 20mL add there is agitator, in dry four-hole boiling flask that thermometer, condenser and nitrogen pass into mouthful, pass into nitrogen, be warming up to 105 ℃ of reactions 6 hours, after having reacted, decompression can obtain double type APEO trisiloxane surfactant after removing toluene.
Embodiment 3
.
Having in the dry four-hole boiling flask that agitator, thermometer, condenser and nitrogen passes into mouthful, add allyl polyethenoxy ether 64.88g, 1, hexamethylene-diisocyanate 12.66g and dibutyl tin laurate 0.39g, pass into nitrogen, is warming up to 75 ℃ of reactions 6 hours.After having reacted, by obtained product 77.51g, 1,1,1,3,5,5,5-heptamethyltrisiloxane 30.21g, platinum catalyst 0.66g and toluene 40mL add there is agitator, in dry four-hole boiling flask that thermometer, condenser and nitrogen pass into mouthful, pass into nitrogen, be warming up to 95 ℃ of reactions 7 hours, after having reacted, decompression can obtain double type APEO trisiloxane surfactant after removing toluene.
Embodiment 4
.
Having in the dry four-hole boiling flask that agitator, thermometer, condenser and nitrogen passes into mouthful, add allyl polyethenoxy ether 25.95g, 1, hexamethylene-diisocyanate 5.12g and dibutyl tin laurate 0.21g, pass into nitrogen, is warming up to 80 ℃ of reactions 5 hours.After having reacted, by obtained product 31.05g, 1,1,1,3,5,5,5-heptamethyltrisiloxane 12.22g, platinum catalyst 0.25g and toluene 25mL add there is agitator, in dry four-hole boiling flask that thermometer, condenser and nitrogen pass into mouthful, pass into nitrogen, be warming up to 110 ℃ of reactions 6 hours, after having reacted, decompression can obtain double type APEO trisiloxane surfactant after removing toluene.
Embodiment 5
.
Having in the dry four-hole boiling flask that agitator, thermometer, condenser and nitrogen passes into mouthful, add allyl polyethenoxy ether 55.61g, 1, hexamethylene-diisocyanate 10.96g and dibutyl tin laurate 0.33g, pass into nitrogen, is warming up to 80 ℃ of reactions 4 hours.After having reacted, by obtained product 66.56g, 1,1,1,3,5,5,5-heptamethyltrisiloxane 26.68g, platinum catalyst 0.58g and toluene 30mL add there is agitator, in dry four-hole boiling flask that thermometer, condenser and nitrogen pass into mouthful, pass into nitrogen, be warming up to 90 ℃ of reactions 8 hours, after having reacted, decompression can obtain double type APEO trisiloxane surfactant after removing toluene.
Embodiment 6
.
Having in the dry four-hole boiling flask that agitator, thermometer, condenser and nitrogen passes into mouthful, add allyl polyethenoxy ether 77.86g, 1, hexamethylene-diisocyanate 15.50g and dibutyl tin laurate 0.62g, pass into nitrogen, is warming up to 75 ℃ of reactions 5 hours.After having reacted, by obtained product 93.32g, 1,1,1,3,5,5,5-heptamethyltrisiloxane 37.86g, platinum catalyst 0.65g and isopropyl alcohol 40mL add there is agitator, in dry four-hole boiling flask that thermometer, condenser and nitrogen pass into mouthful, pass into nitrogen, be warming up to 80 ℃ of reactions 8 hours, after having reacted, decompression can obtain double type APEO trisiloxane surfactant after removing isopropyl alcohol.
Embodiment 7
.
Having in the dry four-hole boiling flask that agitator, thermometer, condenser and nitrogen passes into mouthful, add allyl polyethenoxy ether 13.22g, 1, hexamethylene-diisocyanate 2.62g and dibutyl tin laurate 0.11g, pass into nitrogen, is warming up to 70 ℃ of reactions 6 hours.After having reacted, by obtained product 15.82g, 1,1,1,3,5,5,5-heptamethyltrisiloxane 6.56g, platinum catalyst 0.12g and isopropyl alcohol 10mL add there is agitator, in dry four-hole boiling flask that thermometer, condenser and nitrogen pass into mouthful, pass into nitrogen, be warming up to 80 ℃ of reactions 7 hours, after having reacted, decompression can obtain double type APEO trisiloxane surfactant after removing isopropyl alcohol.
Claims (13)
1. a double type APEO trisiloxane surfactant, is characterized in that having following structural formula:
Wherein n=7-8.
2. the preparation method of a kind of double type APEO trisiloxane surfactant as claimed in claim 1, it is characterized in that: having in the dry four-hole boiling flask that agitator, thermometer, condenser and nitrogen passes into mouthful, add allyl polyethenoxy ether, 1, hexamethylene-diisocyanate and tin catalyst, pass into nitrogen, react a period of time at a certain temperature; After having reacted, by obtained product, 1,1,1,3,5,5,5-heptamethyltrisiloxane, platinum catalyst and solvent add there is agitator, in dry four-hole boiling flask that thermometer, condenser and nitrogen pass into mouthful, pass into nitrogen, react a period of time at a certain temperature, after having reacted, decompression can obtain double type APEO trisiloxane surfactant after removing solvent, and its reaction equation (1) and (2) are as follows:
(1)
(2)
Wherein n=7-8.
3. the preparation method of a kind of double type APEO trisiloxane surfactant as claimed in claim 2, is characterized in that allyl polyethenoxy ether and 1, and the tin catalyst that hexamethylene-diisocyanate reacts required is dibutyl tin laurate.
4. the preparation method of a kind of double type APEO trisiloxane surfactant as claimed in claim 2, it is characterized in that allyl polyethenoxy ether and 1, the amount that hexamethylene-diisocyanate reacts required dibutyl tin laurate is 0.3-1%, is preferably 0.5-0.8%.
5. the preparation method of a kind of double type APEO trisiloxane surfactant as claimed in claim 2, is characterized in that allyl polyethenoxy ether and 1, and mole proportioning of hexamethylene-diisocyanate reaction is 2-2.4:1, is preferably 2-2.1:1.
6. the preparation method of a kind of double type APEO trisiloxane surfactant as claimed in claim 2, is characterized in that allyl polyethenoxy ether and 1, and it is 60-100 ℃ that hexamethylene-diisocyanate reacts required temperature, is preferably 70-80 ℃.
7. the preparation method of a kind of double type APEO trisiloxane surfactant as claimed in claim 2, is characterized in that allyl polyethenoxy ether and 1, and it is 3-8 hour that hexamethylene-diisocyanate reacts the required time, is preferably 4-6 hour.
8. the preparation method of a kind of double type APEO trisiloxane surfactant as claimed in claim 2, it is characterized in that allyl polyethenoxy ether and 1, the product of hexamethylene-diisocyanate reaction, with 1,1,1,3, the aqueous isopropanol that the platinum catalyst that 5,5,5-heptamethyltrisiloxane reacts required is chloroplatinic acid.
9. the preparation method of a kind of double type APEO trisiloxane surfactant as claimed in claim 2, it is characterized in that allyl polyethenoxy ether and 1, the product of hexamethylene-diisocyanate reaction, with 1,1,1,3,5,5, the amount that 5-heptamethyltrisiloxane reacts required platinum catalyst is 0.0008-0.002%, is preferably 0.001-0.0015%.
10. the preparation method of a kind of double type APEO trisiloxane surfactant as claimed in claim 2, it is characterized in that allyl polyethenoxy ether and 1, the product of hexamethylene-diisocyanate reaction, with 1,1,1,3,5,5, mole proportioning of 5-heptamethyltrisiloxane reaction is 1-1.5:2, is preferably 1-1.2:2.
The preparation method of 11. a kind of double type APEO trisiloxane surfactants as claimed in claim 2, it is characterized in that allyl polyethenoxy ether and 1, the product of hexamethylene-diisocyanate reaction, with 1,1,1,3,5,5, it is 60-120 ℃ that 5-heptamethyltrisiloxane reacts required temperature, is preferably 80-110 ℃.
The preparation method of 12. a kind of double type APEO trisiloxane surfactants as claimed in claim 2, it is characterized in that allyl polyethenoxy ether and 1, the product of hexamethylene-diisocyanate reaction, with 1,1,1,3,5,5, it is 4-10 hour that 5-heptamethyltrisiloxane reacts the required time, is preferably 6-8 hour.
The preparation method of 13. a kind of double type APEO trisiloxane surfactants as claimed in claim 2, it is characterized in that allyl polyethenoxy ether and 1, the product of hexamethylene-diisocyanate reaction, with 1,1,1,3, the solvent that 5,5,5-heptamethyltrisiloxane reacts required is any one in toluene or isopropyl alcohol.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110643340A (en) * | 2019-10-14 | 2020-01-03 | 中国石油化工股份有限公司 | High-efficiency water-soluble viscosity-reduction oil washing agent for heavy oil thermal recovery and preparation method thereof |
| CN111808482A (en) * | 2020-07-29 | 2020-10-23 | 广东巴德士化工有限公司 | Water-based multicolor art coating with color changing along with observation angle |
| CN115232276A (en) * | 2022-07-08 | 2022-10-25 | 福建奥翔体育塑胶科技股份有限公司 | Gemini silicon-containing surfactant and preparation method and application thereof |
| CN115869260A (en) * | 2023-02-22 | 2023-03-31 | 四川科宏达集团有限责任公司 | Milk cow nipple medicated bath liquid and preparation method thereof |
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