Novel nonionic surfactant and preparation method thereof
Technical Field
The invention relates to the technical field of surfactants, and particularly relates to a novel surfactant and a preparation method thereof.
Background
The application of the surfactant is very wide, and the surfactant is deeply applied to various civil and industrial fields. The surfactant includes ionic surfactants, nonionic surfactants and the like. Wherein the nonionic surfactant does not ionize in water and is an amphiphilic structure molecule taking hydroxyl or ether bond as hydrophilic group. The nonionic surfactant has the characteristic of non-ionization in water, so that the nonionic surfactant is more excellent than the ionic surfactant in certain aspects, for example, the nonionic surfactant has better solubility in water and organic solvents, has high stability in a solution, is not easily influenced by strong electrolyte inorganic salts, acids and alkalis, and the like. Because the surfactant has good compatibility with other types of surfactants, the surfactant can be mixed with other surfactants for compounding. The nonionic surfactant has the characteristics of good hard water resistance and low foaming property, so that the nonionic surfactant is suitable for being used as a special detergent. In addition, it has important applications in many fields because it has various properties of dispersion, emulsification, foaming, wetting and solubilization.
The fatty alcohol ether is widely used non-ionic surfactant, and has the characteristics of wide raw material source, good biodegradability, strong emulsifying capacity and the like. However, the main problems of the nonionic surfactants are that the comprehensive performance is not excellent enough, low foam, strong emulsification, good low-temperature fluidity and the like cannot be considered, and multiple products are required to be compounded and used in the actual use process.
Therefore, there is still a need in the art for a new nonionic surfactant that can improve low temperature fluidity, reduce foam, and other important properties while maintaining high detergency, oil removal, and emulsification.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a novel nonionic surfactant based on fatty alcohol polyoxyalkyl ether, so as to overcome the limitations of some applications of the prior nonionic surfactant products and simultaneously improve the comprehensive properties of the nonionic surfactant products, such as foam reduction, low-temperature fluidity improvement, pour point reduction, strong emulsifying capacity maintenance and the like.
The above purpose is realized by the following technical scheme:
in a first aspect, there is provided a novel nonionic surfactant having the following general structure (I):
in formula (1), R1 may be one or more selected from saturated or unsaturated hydrocarbon chains having a carbon chain length of 4 to 18 carbon atoms; R2O may be one or more selected from oxyalkylene groups having 2 to 4 carbon atoms; m represents an average molar number of addition of the oxyalkylene group and is an integer or fraction of 3 to 40; n represents an average addition mole number of styrene oxide and is an integer or fraction of more than 0 and not more than 5.
In the technical scheme, as the styrene oxide structure is introduced into the fatty alcohol alkylate, the application performance of the surfactant is improved, so that the low-temperature fluidity of the surfactant is improved and the foam is reduced while the strong decontamination, oil removal and emulsification capabilities are maintained.
The novel nonionic surfactant according to the first aspect, wherein R1 can be one or more selected from the group consisting of C12-14 alkyl, isomeric C13 alkyl, C16-18 alkyl, isooctyl.
The novel nonionic surfactant according to the first aspect, wherein R2O may be one or more selected from oxyethylene, oxypropylene and oxybutylene groups, preferably oxyethylene or oxypropylene groups.
The novel nonionic surfactant according to the first aspect, wherein m is an integer or fraction between 3 and 30, 3 and 20, 3 and 15, 3 and 9, 5 and 30, 5 and 20, 5 and 15, 5 and 9, 9 and 30, 9 and 20, or 9 and 15, preferably 5, 9, or 40.
The novel nonionic surfactant according to the first aspect, wherein n is an integer or fraction of 0.1 to 5, 0.5 to 4, 0.5 to 3, 0.5 to 2, 0.5 to 1, preferably 0.5, 0.8 or 1.
In a second aspect, there is provided a process for the preparation of the novel nonionic surfactant according to the first aspect, comprising the steps of:
taking fatty alcohol ether as an initiator, carrying out quantitative ring-opening addition reaction with styrene oxide for 3-5h at the reaction temperature of 40-120 ℃ under the action of an alkaline catalyst, and then adding acid for neutralization to obtain a nonionic surfactant fatty alcohol polyoxyalkyl polyoxyethyl ether;
wherein the fatty alcohol ether has the general formula:
wherein R1 can be one or more selected from saturated or unsaturated hydrocarbon chains with carbon chain length of 4-18 carbon atoms; R2O may be one or more selected from oxyalkylene groups having 2 to 4 carbon atoms.
With this method, the nonionic surfactant having the above-described novel structure can be obtained. The method has the advantages of simple steps, easily obtained raw materials, mild reaction conditions, short reaction time and the like.
The process according to the second aspect, wherein the basic catalyst is selected from one or more of NaOH, KOH, NaOMe.
The alkaline condition is favorable for opening the ring of the epoxy compound (especially cyclic ether), and especially strong alkaline conditions such as sodium hydroxide, potassium hydroxide and the like. Under the catalytic action of the alkali, the fatty alcohol is dissociated into alcohol anions to attack the epoxy group of the epoxy compound to open the ring, so that the alcohol ether compound is produced.
The process according to the second aspect, the molar ratio of styrene oxide to fatty alcohol ether is from 0.5 to 5:1, preferably 1: 1.
The process according to the second aspect, wherein the reaction temperature is preferably 80 ℃.
At this temperature, the rate of the ring-opening reaction increases due to the ion-pair mechanism of action, which contributes to shortening the reaction time.
Compared with the prior art, the invention has the following advantages:
1. according to the invention, the styrene oxide structure is introduced into the fatty alcohol alkylate, so that the application performance of the fatty alcohol alkylate is improved, the low-temperature fluidity is improved and the foam is reduced while the strong decontamination, oil removal and emulsification capabilities are maintained.
2. The preparation method provided by the invention is simple and convenient, has various forms and wide application range;
3. the nonionic surfactant prepared by the invention has the characteristics of special characteristics and wide application. The novel nonionic surfactant has excellent oil removal, decontamination, emulsification and low foaming performances and good low-temperature fluidity, and can be widely applied to a plurality of fields including but not limited to textile, daily chemical and pesticide industries.
Detailed Description
Some specific embodiments of the present invention will be described below with reference to examples. Those of ordinary skill in the art will appreciate that these examples are provided merely to illustrate how the invention can be practiced and are not intended to limit the scope of the invention in any way.
Fatty alcohol ethers are widely applied nonionic surfactants at present, have the characteristics of wide raw material sources, good biodegradability, strong emulsifying capacity and the like, but have poor comprehensive performance, cannot give consideration to low foam, strong emulsification, good low-temperature fluidity and the like, and need to be compounded with various products in the actual use process. Therefore, the inventors of the present application intend to improve this. Through a large number of practices, the inventors of the present application found that by introducing a styrene oxide structure into a fatty alcohol alkylate, the oil removal, stain removal, emulsification, low foaming properties, etc. of the resulting nonionic surfactant can be improved while having good low temperature fluidity. The present invention has been completed on the basis of this finding.
The novel nonionic surface active agents according to the present invention can be conveniently prepared by the reaction of the following formula (2):
in the formula (2), R1 is a saturated or unsaturated hydrocarbon chain, the carbon chain length is 4-18 carbon atoms, and one or more of the carbon chains can be used; R2O represents oxyalkylene group with 2-4 carbon atoms, which can be one or more; m represents an average molar number of addition of the oxyalkylene group and is an integer or fraction of 3 to 40; n represents an average addition mole number of styrene oxide and is an integer or fraction of more than 0 and not more than 5.
The nonionic surfactant of the present invention will be described and illustrated in more detail with reference to examples. Those of ordinary skill in the art will appreciate that these examples are provided for illustrative purposes only, and that those of ordinary skill in the art will better understand how to implement the present invention and will not set forth any limitations on the scope of the present invention.
Examples
Example 1
This example prepares a nonionic surfactant having the following structural formula (3):
the preparation method of the nonionic surfactant comprises the following steps:
1. stock preparation
C12-14 alcohol polyoxyethylene ether AEO-9 (a commercially available mixed fatty alcohol); styrene oxide (commercially available); catalyst: sodium hydroxide (commercially available).
2. Addition of catalyst
100 g of C12-14 alcohol polyoxyethylene ether AEO-9 is added into a reaction kettle at room temperature, 0.3 g of sodium hydride solid is added into the reaction kettle for nitrogen replacement, and then the reaction kettle is vacuumized to be below-0.09 MPa. Heating the reaction kettle to 100 ℃, and treating for 1h to obtain dehydrated C12-14 alcohol polyoxyethylene ether AEO-9.
3. Addition reaction
And (3) introducing 20 g of styrene oxide into the dehydrated C12-14 alcohol polyoxyethylene ether AEO-9, and carrying out addition reaction for 3h at the temperature of 100 ℃ to obtain an addition product. Finally, 0.2 g of acetic acid neutralization catalyst is added into the reaction kettle to prepare 120.3 g of C12-14 alcohol polyoxyalkyl ether.
4. Performance testing
The C12-14 alcohol polyoxyalkyl ether prepared according to example 1 was tested for emulsifying power, pour point, and foam properties as follows, using commercially available C12-14 alcohol polyoxyethylene ether AEO-9 as control sample 1.
And (3) testing the emulsifying power: preparing 1g/L aqueous solution of a surfactant to be detected, putting 40ml of the liquid to be detected and 5# white oil into a 100ml high-leg beaker respectively, standing in a 100ml measuring cylinder with a plug after the average value is 60s at the rotating speed of 1000r/min of a homogenizer, and recording the time required by 10ml of water phase separated from the lower layer. The longer the time required for delamination, the greater the emulsifying power of the test specimen.
Pour point test: the method is carried out by referring to national standard GB/T3535-2006. Specifically, the sample was heated and then cooled at the cooling rate specified by the national standard, and the fluidity of the sample was observed at every 3 ℃ and the lowest temperature at which the sample was observed to be flowable was recorded as the pour point. The lower the pour point, the better the cold flow, the more convenient it is to use.
And (3) foam testing: preparing 1g/L aqueous solution of a surfactant to be detected, putting 40ml of the solution to be detected in a 100ml measuring cylinder, shaking up and down for 10 times, and recording the height of upper-layer foam (recording the number of milliliters of foam, ml), wherein the larger the numerical value, the higher the foam.
The emulsification, pour point, foam test results are listed in table 1.
Example 2
This example prepares a nonionic surfactant having the following structural formula (4):
the preparation method of the nonionic surfactant comprises the following steps:
1. stock preparation
Isomeric C13 alcohol polyoxyethylene ethers 1315 (commercially available); styrene oxide (commercially available); catalyst: potassium hydroxide (purchased in the market, and conforms to the chemical industry Standard of the people's republic of China GB/T1919-2000).
2. Addition of catalyst
100 g of isomeric C13 alcohol polyoxyethylene ether 1315 is added into a reaction kettle at room temperature, then 0.4 g of 50 percent KOH aqueous solution is added into the reaction kettle for nitrogen replacement, and then the reaction kettle is vacuumized to be below-0.09 MPa. Heating the reaction kettle to 100 ℃, and treating for 1h to obtain dehydrated isomeric C13 alcohol polyoxyethylene ether 1315.
3. Addition reaction
7 g of styrene oxide is pumped into the dehydrated isomeric C13 alcohol polyoxyethylene ether 1315, and the addition reaction is carried out for 1.5h at the temperature of 80 ℃ to obtain an addition product. Finally, 0.2 g of acetic acid as a catalyst for neutralization was added to the reaction vessel to obtain 107.4 g of isomeric tridecanol polyoxyalkyl ether.
4. Performance testing
The isomeric tridecanol polyoxyalkyl ethers prepared in accordance with example 2 were tested for emulsifying power, pour point, and foam properties as follows, using the commercially available isomeric C13 alcohol polyoxyethylene ether 1315 as control sample 2.
And (3) testing the emulsifying power: preparing 1g/L aqueous solution of a surfactant to be detected, putting 40ml of the liquid to be detected and 5# white oil into a 100ml high-leg beaker respectively, standing in a 100ml measuring cylinder with a plug after the average value is 60s at the rotating speed of 1000r/min of a homogenizer, and recording the time required by 10ml of water phase separated from the lower layer. The longer the time required for delamination, the greater the emulsifying power of the test specimen.
Pour point test: the method is carried out by referring to national standard GB/T3535-2006. Specifically, after the sample was heated, it was cooled at a predetermined cooling rate, and the fluidity of the sample was observed at every 3 ℃ and the lowest temperature at which the sample was observed to be able to flow was recorded as the pour point. The lower the pour point, the better the cold flow, the more convenient it is to use.
And (3) foam testing: preparing 1g/L aqueous solution of a surfactant to be detected, putting 40ml of the solution to be detected in a 100ml measuring cylinder, shaking up and down for 10 times, and recording the height of upper-layer foam (recording the number of milliliters of foam, ml), wherein the larger the numerical value, the higher the foam.
The emulsification, pour point, foam results are listed in table 1.
Example 3
This example prepares a nonionic surfactant having the following structural formula (5):
the preparation method of the nonionic surfactant comprises the following steps:
1. stock preparation
C16-18 alcohol polyoxyethylene 6840 (a commercially available mixed alcohol ether); styrene oxide (commercially available); catalyst: NaOMe alcohol solution (commercially available, in accordance with the chemical industry Standard of the people's republic of China HG/T2561-94).
2. Addition of catalyst
100 g of C16-18 alcohol polyoxyethylene ether 6840 is added into a reaction kettle at room temperature, 0.2 g of NaOMe alcohol solution is added into the reaction kettle for nitrogen replacement, and then the reaction kettle is vacuumized to be below-0.09 MPa. Heating the reaction kettle to 100 ℃, and treating for 1h to obtain dehydrated C16-18 alcohol polyoxyethylene ether 6840.
3. Addition reaction
6.5 g of styrene oxide is led into the dehydrated C16-18 alcohol polyoxyethylene ether 6840, and addition reaction is carried out for 1.5h at the temperature of 100 ℃ to obtain an addition product. Finally, 0.1 g of acetic acid neutralizing catalyst was added to the reactor to obtain 106.7 g of C16-18 alcohol polyoxyalkyl ether.
4. Performance testing
The C16-18 alcohol polyoxyalkyl ether prepared according to example 3 was tested for emulsifying power, pour point, and foam properties as follows, using the commercially available C16-18 alcohol polyoxyethylene 6840 as control sample 3.
And (3) testing the emulsifying power: preparing 1g/L aqueous solution of a surfactant to be detected, putting 40ml of the liquid to be detected and 5# white oil into a 100ml high-leg beaker respectively, standing in a 100ml measuring cylinder with a plug after the average value is 60s at the rotating speed of 1000r/min of a homogenizer, and recording the time required by 10ml of water phase separated from the lower layer. The longer the time required for delamination, the greater the emulsifying power of the test specimen.
Pour point test: the method is carried out by referring to national standard GB/T3535-2006. Specifically, the sample was heated and then cooled at a predetermined cooling rate, and the fluidity of the sample was observed at every 3 ℃ and the lowest temperature at which the sample was observed to be able to flow was recorded as the pour point. The lower the pour point, the better the cold flow, the more convenient it is to use.
And (3) foam testing: preparing 1g/L aqueous solution of a surfactant to be detected, putting 40ml of the solution to be detected in a 100ml measuring cylinder, shaking up and down for 10 times, and recording the height of upper-layer foam (recording the number of milliliters of foam, ml), wherein the larger the numerical value, the higher the foam.
The emulsification, pour point, foam test results are listed in table 1.
Example 4
This example prepares a nonionic surfactant having the following structural formula (6):
the preparation method of the nonionic surfactant comprises the following steps:
1. stock preparation
Isooctanol polyoxyalkyl ether EH9 (commercially available as a finished mixture); styrene oxide (commercially available); catalyst: potassium hydroxide (commercially available, chemical industry Standard of the people's republic of China GB/T1919-2000).
2. Addition of catalyst
100 g of isooctanol polyoxy alkyl ether EH9 is added into a reaction kettle at room temperature, 0.2 g of KOH solid is added into the reaction kettle for nitrogen replacement, and then the reaction kettle is vacuumized to be below-0.09 MPa. Heating the reaction kettle to 100 ℃ after starting heating, and obtaining dehydrated isooctanol polyoxyalkyl ether EH9 after treating for 1 h.
3. Addition reaction
And (3) introducing 12 g of styrene oxide into the dehydrated isooctanol polyoxyalkyl ether EH9, and carrying out addition reaction for 1.5h at the temperature of 80 ℃ to obtain an addition product. And finally, adding acetic acid into the reaction kettle for neutralization reaction to obtain 112.2 g of isooctanol polyoxyalkyl ether.
4. Performance testing
The emulsifying ability, pour point and foam properties of the isooctanol polyoxyalkylene ether prepared according to example 4 were tested as follows, using commercially available isooctanol polyoxyalkylene ether EH9 as control sample 4.
The emulsifying power testing method comprises the following steps: preparing 1g/L aqueous solution of a surfactant to be detected, putting 40ml of the liquid to be detected and 5# white oil into a 100ml high-leg beaker respectively, standing in a 100ml measuring cylinder with a plug after the average value is 60s at the rotating speed of 1000r/min of a homogenizer, and recording the time required by 10ml of water phase separated from the lower layer. The longer the time required for delamination, the greater the emulsifying power of the test specimen.
Pour point test: the method is carried out according to the reference GB/T3535-2006. Specifically, the sample was heated and then cooled at a predetermined cooling rate, and the fluidity of the sample was observed at every 3 ℃ and the lowest temperature at which the sample was observed to be flowable was recorded as the pour point. The lower the pour point, the better the cold flow, the more convenient it is to use.
And (3) foam testing: preparing 1g/L aqueous solution of a surfactant to be detected, putting 40ml of the solution to be detected in a 100ml measuring cylinder, shaking up and down for 10 times, and recording the height of upper-layer foam (recording the number of milliliters of foam, ml), wherein the larger the numerical value, the higher the foam. The emulsification, pour point, foam results are shown in table 1.
TABLE 1 emulsification, pour point and foam of fatty alcohol polyoxyalkylene ether nonionic surfactants
Examples
|
Emulsifying power/s
|
Pour point/. degree.C
|
Height of foam, ml
|
1<1>
|
1470
|
5
|
26
|
2<0.5>
|
1340
|
10
|
30
|
3<1>
|
1855
|
10
|
35
|
4<0.8>
|
900
|
7
|
27
|
Comparative example AEO9
|
1230
|
22
|
>60
|
Comparative example 1315
|
1140
|
28
|
>60
|
Comparative example 6840
|
1565
|
40
|
>60
|
Comparative example EH9
|
950
|
12
|
44 |
As can be seen from Table 1, the novel nonionic surfactant prepared by the invention has excellent comprehensive application performance in emulsification, foam, pour point and the like, and has great application potential.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included therein.