CN105561865A - Non-ionic oligomeric surfactant and preparation method thereof - Google Patents
Non-ionic oligomeric surfactant and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a non-ionic oligomeric surfactant which is of a structure as shown in the formula (I) or the formula (II) as shown in the description. The invention further relates to a preparation method of the non-ionic oligomeric surfactant, and the non-ionic oligomeric surfactant prepared by using the preparation method. The non-ionic oligomeric surfactant provided by the invention is very good in oil removing property and relatively good in property of reducing tension of an oil-water interface.
Description
Technical field
The present invention relates to a kind of nonionic oligo surfactant, and a kind of preparation method of nonionic oligo surfactant and the nonionic oligo surfactant of preparation thereof.
Background technology
The molecular structure of oligo surfactant is between traditional strand, between double linked list surface-active agent and high molecular surfactant molecule, and its structure can be regarded as spacer group and is connected by three to ten several strand surfactant molecules and form.Oligomeric-type surfactant is expected to become the low and effective surfactant of new generation of consumption, it is advantageous that: single linked list surface-active agent has critical micelle concentration low relatively, good surface-active, and rheological property is various; Compare its rate of dispersion of high molecular surfactant fast, anti-shear performance is good.
Classify from spatial configuration of molecules, oligo surfactant molecule can be divided into and upwards extending at one-dimensional square, is similar to the chain structure of dressing molecule, and the branching type structure that stretches on three-dimensional.
At present, tertiary oil recovery field adopts the oligo surfactant of chain structure mostly, but the oligo surfactant of chain structure causes its oil removing ability lower due to the reason of structure, and the effect in tertiary oil recovery field is unsatisfactory.
Therefore, urgent need is a kind of now can effectively improve oligo surfactant of oil removing ability and preparation method thereof.
Summary of the invention
The defect that the oil removing ability in order to overcome oligo surfactant in prior art of the object of the invention is is low, the nonionic oligo surfactant that a kind of oil removing ability is high is provided, and a kind of preparation method of nonionic oligo surfactant and the nonionic oligo surfactant of preparation thereof.
The present inventor finds under study for action, and nonionic oligo surfactant has as shown in the formula the structure shown in (I) or formula (II)
Wherein, m is the arbitrary integer in 1-50, and n is the arbitrary integer in 2-8, R
1for C
4-C
20alkyl, R
2for polyethers, the monomer forming described polyethers is oxirane and/or expoxy propane, and the degree of polymerization of described polyethers is 5-100.
Therefore, to achieve these goals, on the one hand, the invention provides a kind of nonionic oligo surfactant, this surfactant has formula (I) or the structure shown in formula (II),
Wherein, m is the arbitrary integer in 1-50, and n is the arbitrary integer in 2-8, R
1for C
4-C
20alkyl, R
2for polyethers, the monomer forming described polyethers is oxirane and/or expoxy propane, and the degree of polymerization of described polyethers is 5-100.
On the other hand, present invention also offers a kind of preparation method of nonionic oligo surfactant, the method comprises:
(1) under phenol-formaldehyde reaction condition, by structure for the compound shown in formula (III) or (IV) and structure for the compound shown in formula (V) carries out phenol-formaldehyde reaction;
(2) under polycondensation reaction condition, the product obtain step (1) and formaldehyde, structure carry out polycondensation reaction for the compound shown in formula (III) or (IV);
(3) under addition reaction condition, the product obtain step (2) and epoxyalkane carry out addition reaction;
Wherein, R
1for C
4-C
20alkyl, n is the arbitrary integer in 2-8,
Wherein, in step (2), the product that step (1) obtains and formaldehyde, structure for the mol ratio of the compound shown in formula (III) or (IV) be 1:4-85:4-85; In step (3), the mol ratio of the product that step (2) obtains and epoxyalkane is 1:70-320, and wherein, described epoxyalkane is oxirane and/or expoxy propane.
The third aspect, present invention also offers nonionic oligo surfactant prepared by said method.
Nonionic oligo surfactant of the present invention has higher oil removing ability, and the ability reducing oil water interfacial tension is also stronger.
Other features and advantages of the present invention are described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Fig. 1 is the hydrogen spectrum spectrogram of the intermediate product of embodiment 1;
Fig. 2 is the carbon spectrum spectrogram of the intermediate product of embodiment 1;
Fig. 3 is the mass spectrogram of the intermediate product of embodiment 1.
Detailed description of the invention
Below the specific embodiment of the present invention is described in detail.Should be understood that, detailed description of the invention described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
On the one hand, the invention provides a kind of nonionic oligo surfactant, this surfactant has formula (I) or the structure shown in formula (II),
Wherein, m is the arbitrary integer in 1-50, and n is the arbitrary integer in 2-8, R
1for C
4-C
20alkyl, R
2for polyethers, the monomer forming described polyethers is oxirane and/or expoxy propane, and the degree of polymerization of described polyethers is 5-100.
According to surfactant of the present invention, wherein, as long as nonionic oligo surfactant has above-mentioned formula (I) or the structure shown in formula (II), wherein, m is the arbitrary integer in 1-50, and n is the arbitrary integer in 2-8, R
1for C
4-C
20alkyl, R
2for polyethers, the monomer forming described polyethers is oxirane and/or expoxy propane, the degree of polymerization of described polyethers is 5-100, object of the present invention can be realized, namely there is higher oil removing ability, but in order to the oil removing ability improving nonionic oligo surfactant is further gone forward side by side the low reduction oil water interfacial tension of a step-down, preferably, m is the arbitrary integer in 1-19.
According to surfactant of the present invention, wherein, preferably, when the degree of polymerization of described polyethers is 7-50, the oil removing ability that can improve nonionic oligo surfactant is further gone forward side by side the low reduction oil water interfacial tension of a step-down.
On the other hand, present invention also offers a kind of preparation method of nonionic oligo surfactant, the method comprises:
(1) under phenol-formaldehyde reaction condition, by structure for the compound shown in formula (III) or (IV) and structure for the compound shown in formula (V) carries out phenol-formaldehyde reaction;
(2) under polycondensation reaction condition, the product obtain step (1) and formaldehyde, structure carry out polycondensation reaction for the compound shown in formula (III) or (IV);
(3) under addition reaction condition, the product obtain step (2) and epoxyalkane carry out addition reaction;
Wherein, R
1for C
4-C
20alkyl, n is the arbitrary integer in 2-8,
Wherein, in step (2), the product that step (1) obtains and formaldehyde, structure for the mol ratio of the compound shown in formula (III) or (IV) be 1:4-85:4-85; In step (3), the mol ratio of the product that step (2) obtains and epoxyalkane is 1:70-320, and wherein, described epoxyalkane is oxirane and/or expoxy propane.
According to preparation method of the present invention, wherein, in step (1), phenol-formaldehyde reaction condition preferably includes: carry out in presence of an acid, and temperature is 100-130 DEG C, and the time is 1-2 hour.
It should be appreciated by those skilled in the art, the phenol-formaldehyde reaction condition of step (1) can also comprise: carry out in a solvent.Wherein, described solvent can be the organic solvent of this area routine, such as, can be at least one in decahydronaphthalene, two methyl phenyl ethers anisoles and dimethylbenzene.As long as the consumption of solvent can abundant solubilizing reaction raw material, phenol-formaldehyde reaction is carried out in a solvent, and be conventional quantity of solvent, this is conventionally known to one of skill in the art, does not repeat them here.
According to preparation method of the present invention, wherein, in step (1), structure for the compound shown in formula (III) or (IV) and structure for the mol ratio of the compound shown in formula (V) is preferably 1:0.05-0.25.
It will be understood by those skilled in the art that acid serves as catalyst, for the consumption of acid in step (1), as long as be conventional catalytic amount, preferably, with structure for the molal quantity of the compound shown in formula (V) is benchmark, the consumption of acid is 0.1-1.5 % by mole.
What it should be appreciated by those skilled in the art is, in order to reduce the water that generates in phenol-formaldehyde reaction to the impact of follow-up polycondensation reaction, also need to carry out post processing after step (1) phenol-formaldehyde reaction, the mode of post processing preferably includes: under 0.04-0.1MPa, steam water at 50-95 DEG C, then 20-50 DEG C is cooled to, wherein, while steaming water, solvent also can partly be steamed, utilize water different with the boiling point of solvent come recycling design, and recovered solvent is added to again the solvent as follow-up polycondensation reaction in reaction system after phenol-formaldehyde reaction terminates.
According to preparation method of the present invention, wherein, in step (2), polycondensation reaction condition preferably includes: carry out in presence of an acid, and temperature is 90-110 DEG C, and the time is 2-4 hour.
It should be appreciated by those skilled in the art, the polycondensation reaction condition of step (2) can also comprise: carry out in a solvent.Wherein, described solvent can be the organic solvent of this area routine, such as, can be at least one in decahydronaphthalene, two methyl phenyl ethers anisoles and dimethylbenzene.As long as the consumption of solvent can abundant solubilizing reaction raw material, polycondensation reaction is carried out in a solvent, and be conventional quantity of solvent, this is conventionally known to one of skill in the art, does not repeat them here.
According to preparation method of the present invention, wherein, in step (2), the product that step (1) obtains and formaldehyde, structure is preferably 1:7-32:6-30 for the mol ratio of the compound shown in formula (III) or (IV), the product obtained when step (1) and formaldehyde, when the mol ratio that structure is the compound shown in formula (III) or (IV) is 1:7-32:6-30, m in the structural formula (I) of obtained nonionic oligo surfactant or (II) is the arbitrary integer in 1-19, the low oil water interfacial tension of a step-down thus the oil removing ability that can improve nonionic oligo surfactant is further gone forward side by side.
It will be understood by those skilled in the art that acid serves as catalyst, for the consumption of acid in step (2), as long as be conventional catalytic amount, preferably, the molal quantity of the product obtained with step (1) is for benchmark, and the consumption of acid is 0.1-1.5 % by mole.
What it should be appreciated by those skilled in the art is, in order to reduce the water that generates in polycondensation reaction to the impact of follow-up addition reaction, also need to carry out post processing after step (2) polycondensation reaction, the mode of post processing preferably includes: under 0.04-0.1MPa, steam water at 50-95 DEG C, then 20-50 DEG C is cooled to, wherein, while steaming water, solvent also can partly be steamed, utilize water different with the boiling point of solvent come recycling design, and recovered solvent is added to again the solvent as follow-up addition reaction in reaction system after polycondensation reaction terminates.
According to preparation method of the present invention, wherein, the acid in step (1) and step (2) is all preferably at least one in the concentrated sulfuric acid, concentrated hydrochloric acid and organic acid, and organic acid is preferably toluene sulfonic acide and/or DBSA.Wherein, the kind of the acid in the kind of the acid in step (2) and step (1) can be the same or different, and in order to simple to operate, the kind of acid in step (2) is identical with kind sour in step (1).It should be appreciated by those skilled in the art and be, the concentrated sulfuric acid is H
2sO
4concentration be more than or equal to 70 % by weight sulphur aqueous acid, in the present invention, the concentrated sulfuric acid is the concentrated sulfuric acid of 70-98 % by weight, is preferably the concentrated sulfuric acid of 95-98 % by weight.
According to preparation method of the present invention, wherein, in step (3), addition reaction condition preferably includes: carry out in the presence of a base with under inert atmosphere, and temperature is 130-160 DEG C, and the time is 1-4 hour.
It should be appreciated by those skilled in the art, the addition reaction condition of step (3) can also comprise: carry out in a solvent.Wherein, described solvent can be the organic solvent of this area routine, such as, can be at least one in decahydronaphthalene, two methyl phenyl ethers anisoles and dimethylbenzene.As long as the consumption of solvent can abundant solubilizing reaction raw material, addition reaction is carried out in a solvent, and be conventional quantity of solvent, this is conventionally known to one of skill in the art, does not repeat them here.
According to preparation method of the present invention, wherein, in step (3), the mol ratio of the product that step (2) obtains and epoxyalkane is preferably 1:170-290, when the mol ratio of the product that step (2) obtains and epoxyalkane is 1:170-290, the degree of polymerization of the polyethers in the structural formula (I) of obtained nonionic oligo surfactant or (II) is 7-50, the low oil water interfacial tension of a step-down thus the oil removing ability that can improve nonionic oligo surfactant is further gone forward side by side.
It will be understood by those skilled in the art that alkali serves as catalyst in step (3), for the consumption of alkali, as long as be conventional catalytic amount, preferably, the molal quantity of the product obtained with step (2) is for benchmark, and the consumption of alkali is 0.5-4 % by mole.
According to preparation method of the present invention, wherein, the alkali in step (3) is preferably at least one in NaOH, potassium hydroxide and calcium hydroxide.
It will be understood by those skilled in the art that inert atmosphere can be provided by inert gas, such as, can be provided by the one in nitrogen, helium and neon, preferably provided by nitrogen.
In the present invention, during practical operation, conveniently, in step (3) addition reaction terminal determination methods can for be incubated at 130-160 DEG C after adding epoxyalkane no longer decline to pressure after be incubated 0.5 hour again.
The third aspect, the invention provides the nonionic oligo surfactant prepared by said method.
In the present invention, can be composed by hydrogen, carbon spectrum and mass spectroscopy determine to prepare intermediate product in nonionic oligo surfactant process and the structural formula of nonionic oligo surfactant, the method of hydrogen spectrum, carbon spectrum and mass spectroscopy is known to the skilled person, and does not repeat them here.
Embodiment
In the following Examples and Comparative Examples, molecular weight refers to number-average molecular weight, and vapor-pressure osmometry is measured and carried out with reference to People's Republic of China (PRC) standard GB6597-86 method.
Embodiment 1
The present embodiment is for illustration of nonionic oligo surfactant of the present invention and preparation method thereof.
Dissolved in the decahydronaphthalene of 200 weight portions by 98 % by weight concentrated sulfuric acids of the 4-nonyl phenol of 1000 weight portions, the butanedial of 86 weight portions and 1 weight portion, at 100 DEG C, react 1h, be then 0.06MPa at pressure, temperature is steam water at 75 DEG C, is cooled to 40 DEG C; The organic solvent steamed is reclaimed and is again added in reaction system, then add the formaldehyde of 720 weight portions and the 4-nonyl phenol of 5280 weight portions, at 90 DEG C, carry out reaction 3h, then be 0.06MPa at pressure, temperature is steam water at 75 DEG C, is cooled to 25 DEG C, obtains intermediate product; The organic solvent steamed is reclaimed and is again added in reaction system, add the NaOH of 150 weight portions again, and in a nitrogen atmosphere, pass into the oxirane of 12320 weight portions, be incubated at 130 DEG C and be incubated 0.5h again after no longer declining to pressure and namely show that addition reaction terminates, the nonionic oligo surfactant A1 of obtained oily liquids.
Hydrogen spectrum, carbon spectrum and mass spectroscopy are carried out respectively to above-mentioned intermediate product, the hydrogen spectrum of intermediate product, carbon are composed and mass spectroscopy result is distinguished as shown in Figure 1, Figure 2 and Figure 3, can be inferred by above-mentioned spectrogram, the structural formula of intermediate product is as shown in (VI), the molecular weight adopting vapor-pressure osmometry to record nonionic oligo surfactant A1 is 18500, therefore, the structural formula of A1 is as shown in (VII).
Embodiment 2
The present embodiment is for illustration of nonionic oligo surfactant of the present invention and preparation method thereof.
The toluene sulfonic acide of the 2-nonyl phenol of 1000 weight portions, the MDA of 72 weight portions and 30 weight portions is dissolved in the dimethylbenzene of 250 weight portions, phenol-formaldehyde reaction 1h is carried out at 110 DEG C, then be 0.1MPa at pressure, temperature is steam water at 95 DEG C, is cooled to 50 DEG C; The organic solvent steamed is reclaimed and is again added in reaction system, then add the formaldehyde of 960 weight portions and the 2-nonyl phenol of 7040 weight portions, at 100 DEG C, carry out polycondensation reaction 4h, then be 0.1MPa at pressure, temperature is steam water at 95 DEG C, is cooled to 20 DEG C, obtains intermediate product; The organic solvent steamed is reclaimed and is again added in reaction system, add the potassium hydroxide of 120 weight portions again, and in a nitrogen atmosphere, pass into the oxirane of 12675 weight portions, be incubated at 145 DEG C and be incubated 0.5h again after no longer declining to pressure and namely show that addition reaction terminates, the nonionic oligo surfactant A2 of obtained oily liquids.
Hydrogen spectrum, carbon spectrum and mass spectroscopy are carried out respectively to above-mentioned intermediate product, the hydrogen of intermediate product is composed, carbon is composed and mass spectrogram is unlisted, the structural formula of intermediate product is inferred by the spectrogram measured, the molecular weight adopting vapor-pressure osmometry to record nonionic oligo surfactant A2 is 20600, therefore, the structural formula of A2 is as shown in (VIII).
Embodiment 3
The present embodiment is for illustration of nonionic oligo surfactant of the present invention and preparation method thereof.
The butanedial of the 4-TBP of 700 weight portions, 86 weight portions and the DBSA of 11 weight portions are dissolved in two methyl phenyl ethers anisoles of 30 weight portions, phenol-formaldehyde reaction 1.5h is carried out at 130 DEG C, then be 0.05MPa at pressure, temperature is steam water at 65 DEG C, is cooled to 30 DEG C; The organic solvent steamed is reclaimed and is again added in reaction system, add the formaldehyde of 720 weight portions and the 4-TBP of 4500 weight portions more simultaneously, polycondensation reaction 2.5h is carried out at 110 DEG C, then be 0.05MPa at pressure, temperature is steam water at 65 DEG C, be cooled to 30 DEG C, obtain intermediate product; The organic solvent steamed is reclaimed and is again added in reaction system, add the calcium hydroxide of 40 weight portions again, and in a nitrogen atmosphere, pass into the oxirane of 8624 weight portions, be incubated at 160 DEG C and be incubated 0.5h again after no longer declining to pressure and namely show that addition reaction terminates, the nonionic oligo surfactant A3 of obtained oily liquids.
Hydrogen spectrum, carbon spectrum and mass spectroscopy are carried out respectively to above-mentioned intermediate product, the hydrogen of intermediate product is composed, carbon is composed and mass spectrogram is unlisted, the structural formula of intermediate product is inferred by the spectrogram measured, the molecular weight adopting vapor-pressure osmometry to record nonionic oligo surfactant A3 is 7200, therefore, the structural formula of A3 is as shown in (Ⅸ).
Embodiment 4
The present embodiment is for illustration of nonionic oligo surfactant of the present invention and preparation method thereof.
Nonionic oligo surfactant is prepared according to the method for embodiment 1, unlike, relative to the 4-nonyl phenol that the phenol-formaldehyde reaction of 1000 weight portions initially adds, in polycondensation reaction, the addition of formaldehyde, 4-nonyl phenol is respectively 2520,18480, namely in polycondensation reaction, the mol ratio of phenol-formaldehyde reaction product and formaldehyde, contraposition alkylphenol is 1:84:84, the nonionic oligo surfactant A4 of obtained oily liquids.
Hydrogen spectrum, carbon spectrum and mass spectroscopy are carried out respectively to above-mentioned intermediate product, the hydrogen of intermediate product is composed, carbon is composed and mass spectrogram is unlisted, the structural formula of intermediate product is inferred by the spectrogram measured, the molecular weight adopting vapor-pressure osmometry to record nonionic oligo surfactant A4 is 58000, therefore, the structural formula of A4 is as shown in (Ⅹ).
Embodiment 5
The present embodiment is for illustration of nonionic oligo surfactant of the present invention and preparation method thereof.
Nonionic oligo surfactant is prepared according to the method for embodiment 1, unlike, relative to the 4-nonyl phenol that the phenol-formaldehyde reaction of 1000 weight portions initially adds, the addition of oxirane is 7392 weight portions, namely in addition reaction, the mol ratio of polycondensation product and oxirane is 1:168, the nonionic oligo surfactant A5 of obtained oily liquids.
Hydrogen spectrum, carbon spectrum and mass spectroscopy are carried out respectively to above-mentioned intermediate product, the hydrogen of intermediate product is composed, carbon is composed and mass spectrogram is unlisted, the structural formula of intermediate product is inferred by the spectrogram measured, the molecular weight adopting vapor-pressure osmometry to record nonionic oligo surfactant A5 is 13600, therefore, the structural formula of A5 is as shown in (Ⅺ).
Comparative example 1
Commercially available nonionic surface active agent NP-10 (purchased from Tao Shi chemical industry), by its called after D1, its structural formula is
Comparative example 2
The chain type oligomeric-type surfactant molecule tert-butyl phenol formaldehyde APEO-9 of preparation, by its called after D2, concrete preparation method is: dissolved in the dimethylbenzene of 100 weight portions by 98 % by weight concentrated sulfuric acids of the 4-tert-butyl phenol of 328 weight portions, the formaldehyde of 60 weight portions and 1 weight portion, 3h is reacted at 100 DEG C, then be 0.06MPa at pressure, temperature is steam water at 75 DEG C, is cooled to 40 DEG C; Add the potassium hydroxide of 8 weight portions, and in a nitrogen atmosphere, pass into the oxirane of 846 weight portions, be incubated at 130 DEG C and be incubated 0.5h again after no longer declining to pressure and namely show that addition reaction terminates, can obtain tert-butyl phenol formaldehyde APEO-9, its structural formula is:
Comparative example 3
The nonyl phenol formaldehyde condensation products APEO-15 of preparation, by its called after D3, concrete preparation method is: dissolved in the dimethylbenzene of 100 weight portions by 98 % by weight concentrated sulfuric acids of the 4-nonyl phenol of 530 weight portions, the formaldehyde of 60 weight portions and 1 weight portion, 3h is reacted at 100 DEG C, then be 0.06MPa at pressure, temperature is steam water at 75 DEG C, is cooled to 40 DEG C; Add the potassium hydroxide of 8 weight portions, and in a nitrogen atmosphere, pass into the oxirane of 1480 weight portions, be incubated at 130 DEG C and be incubated 0.5h again after no longer declining to pressure and namely show that addition reaction terminates, can obtain nonyl phenol formaldehyde condensation products APEO-15, its structural formula is:
Test case
Test case 1
The nonionic oligo surfactant A1-A5 adopting the method in China PetroChemical Corporation company standard Q/SHCG11-2011 to prepare embodiment 1-5 and the surfactant D 1-D3 of comparative example 1-3 carries out static washing oil rate performance evaluation, and measurement result is in table 1.
Table 1
Test case 2
Oil water interfacial tension mensuration is carried out according to the surfactant D 1-D3 rotating nonionic oligo surfactant A1-A5 that the method for dripping prepared embodiment 1-5 and comparative example 1-3 in People's Republic of China (PRC) oil and gas industry standard SY-T5370-1999.
Table 2
Compared with comparative example 1-3 by embodiment 1-5 and can find out, the static washing oil rate of nonionic oligo surfactant of the present invention is higher, and the ability reducing oil water interfacial tension is also stronger.
Embodiment 1 is compared can find out with embodiment 4, the product obtained when step (1) and formaldehyde, structure for the mol ratio of the compound shown in formula (III) or (IV) be 1:7-32:6-30, namely, when the m in nonionic oligo surfactant structural formula (I) or (II) is the arbitrary integer in 1-19, the oil removing ability that can improve obtained nonionic oligo surfactant is further gone forward side by side the low oil water interfacial tension of a step-down.
Embodiment 1 is compared can find out with embodiment 5, the product obtained when step (2) and the mol ratio of epoxyalkane are 1:170-290, when the degree of polymerization of the polyethers namely in nonionic oligo surfactant structural formula (I) or (II) is 7-50, the oil removing ability that can improve obtained nonionic oligo surfactant is further gone forward side by side the low oil water interfacial tension of a step-down.
Nonionic oligo surfactant of the present invention has the ability of higher oil removing ability and stronger reduction oil water interfacial tension.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned detailed description of the invention, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible combination.
In addition, also can be combined between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (16)
1. a nonionic oligo surfactant, is characterized in that, this surfactant has formula (I) or the structure shown in formula (II),
Wherein, m is the arbitrary integer in 1-50, and n is the arbitrary integer in 2-8, R
1for C
4-C
20alkyl, R
2for polyethers, the monomer forming described polyethers is oxirane and/or expoxy propane, and the degree of polymerization of described polyethers is 5-100.
2. surfactant according to claim 1, wherein, m is the arbitrary integer in 1-19.
3. surfactant according to claim 1, wherein, the degree of polymerization of described polyethers is 7-50.
4. a preparation method for nonionic oligo surfactant, is characterized in that, the method comprises:
(1) under phenol-formaldehyde reaction condition, by structure for the compound shown in formula (III) or (IV) and structure for the compound shown in formula (V) carries out phenol-formaldehyde reaction;
(2) under polycondensation reaction condition, the product obtain step (1) and formaldehyde, structure carry out polycondensation reaction for the compound shown in formula (III) or (IV);
(3) under addition reaction condition, the product obtain step (2) and epoxyalkane carry out addition reaction;
Wherein, R
1for C
4-C
20alkyl, n is the arbitrary integer in 2-8,
Wherein, in step (2), the product that step (1) obtains and formaldehyde, structure for the mol ratio of the compound shown in formula (III) or (IV) be 1:4-85:4-85; In step (3), the mol ratio of the product that step (2) obtains and epoxyalkane is 1:70-320, and wherein, described epoxyalkane is oxirane and/or expoxy propane.
5. preparation method according to claim 4, wherein, in step (1), described phenol-formaldehyde reaction condition comprises: carry out in presence of an acid, and temperature is 100-130 DEG C, and the time is 1-2 hour.
6. preparation method according to claim 4, wherein, in step (2), described polycondensation reaction condition comprises: carry out in presence of an acid, and temperature is 90-110 DEG C, and the time is 2-4 hour.
7. preparation method according to claim 4, wherein, in step (3), described addition reaction condition comprises: carry out in the presence of a base with under inert atmosphere, and temperature is 130-160 DEG C, and the time is 1-4 hour.
8. according to the preparation method in claim 3-7 described in any one, wherein, in step (1), structure for the compound shown in formula (III) or (IV) and structure for the mol ratio of the compound shown in formula (V) is 1:0.05-0.25.
9. preparation method according to claim 5, wherein, with structure for the molal quantity of the compound shown in formula (V) is benchmark, the consumption of acid is 0.1-1.5 % by mole.
10. according to the preparation method in claim 3-7 described in any one, wherein, in step (2), the product that step (1) obtains and formaldehyde, structure for the mol ratio of the compound shown in formula (III) or (IV) be 1:7-32:6-30.
11. preparation methods according to claim 6, wherein, the molal quantity of the product obtained with step (1) is for benchmark, and the consumption of acid is 0.1-1.5 % by mole.
12. preparation methods according to claim 5,6,9 or 11, wherein, described acid is at least one in the concentrated sulfuric acid, concentrated hydrochloric acid and organic acid, and preferably, described organic acid is toluene sulfonic acide and/or DBSA.
13. according to the preparation method in claim 3-7 described in any one, and wherein, in step (3), the mol ratio of the product that step (2) obtains and epoxyalkane is 1:170-290.
14. preparation methods according to claim 7, wherein, the molal quantity of the product obtained with step (2) is for benchmark, and the consumption of alkali is 0.5-4 % by mole.
15. preparation methods according to claim 7 or 14, wherein, described alkali is at least one in NaOH, potassium hydroxide and calcium hydroxide.
The 16. nonionic oligo surfactants prepared by method described in any one in claim 4-15.
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| CN1879955A (en) * | 2005-06-14 | 2006-12-20 | 天津科技大学 | Use of anion geminal surfactant waste paper deinking agent and composition |
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| CN1879955A (en) * | 2005-06-14 | 2006-12-20 | 天津科技大学 | Use of anion geminal surfactant waste paper deinking agent and composition |
Non-Patent Citations (2)
| Title |
|---|
| CAROLINE SEGUIN: "Aleternative non-aqueous water-miscible solvents for surfactants", 《COLLOIDS AND SURFACES》 * |
| 黄海龙: "聚烷基酚聚氧乙烯醚型表面活性剂的表面性能分析", 《世界农药》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112724981A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Petroleum-polluted soil eluting agent composition and preparation method thereof |
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