CN107376778A - A kind of polyoxyethylene sulfonic acid salt form Gemini surface active agent and preparation method thereof - Google Patents

A kind of polyoxyethylene sulfonic acid salt form Gemini surface active agent and preparation method thereof Download PDF

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CN107376778A
CN107376778A CN201710446110.4A CN201710446110A CN107376778A CN 107376778 A CN107376778 A CN 107376778A CN 201710446110 A CN201710446110 A CN 201710446110A CN 107376778 A CN107376778 A CN 107376778A
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sulfonic acid
preparation
salt form
acid salt
surface active
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刘治田
周泽坤
张旗
王璇
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China Petroleum and Natural Gas Co Ltd
Wuhan Institute of Technology
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China Petroleum and Natural Gas Co Ltd
Wuhan Institute of Technology
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Abstract

The present invention provides a kind of polyoxyethylene sulfonic acid salt form Gemini surface active agent and preparation method thereof.The polyoxyethylene sulfonic acid salt form Gemini surface active agent structural formula shown in formula I, wherein：N values are 6,7,8,9,10,12 or 14；M values are 4,5,6,7,8,9,10,15 or 20.There is the preparation method of polyoxyethylene sulfonic acid salt form Gemini surface active agent provided by the invention raw material to be easy to get, reaction condition is gentle, preparation technology is simple, polyoxyethylene sulfonic acid salt form Gemini surface active agent purity height, the yield being prepared are high, with physicochemical properties such as good salt-resistances and heat-resisting quantity, oil recovery factor can be effectively improved in the exploitation of the Complex Reservoirs such as high temperature, high salinity by applying, and be had broad application prospects in field of petroleum exploitation.

Description

A kind of polyoxyethylene sulfonic acid salt form Gemini surface active agent and preparation method thereof
Technical field
The invention belongs to technical field of surfactant, be related to a kind of polyoxyethylene sulfonic acid salt form Gemini surface active agent and Its preparation method.
Background technology
In recent years, the Gemini surfaces linked up 2 conventional surfactant molecules by chemical bond by connection base Activating agent research is very active.Compared with traditional surfactant, Gemini surface active has higher surface-active, very Low Krafft points and good water solubility, its molecular weight generally between conventional surfactant and high molecular surfactant it Between, it is described as surfactant of new generation.
It is divided into anion, cation, nonionic and amphoteric by the different Gemini surface actives of hydrophilic group, wherein Anionic type Gemini surface active agent is divided into sulfonate type, sulfate type, carboxylic acid type and phosphate type again.Sulfonate type Gemini surface active activity is high, and heat endurance is good, has preferable salt-resistance, Interfacial Adsorption amount is small, in less concentration Under can significantly reduce oil water interfacial tension.
Sulfonate type dimeric surfactant be by two sulfosalt surfactant monomers by covalent bond close-coupled, So as to prevent the hydrophilic head base electrostatic repulsion in the orderly accumulation process of surfactant, the hydrophobic association of hydrocarbon interchain is enhanced Effect, many physical and chemical performances for being different from conventional surfactant are made it have, grinding into colloid and interface science field Study carefully focus.At present, phase of basic research is also in such surfactant both at home and abroad, emphasis still concentrates on the exploitation of new varieties And physical and chemical performance research, but the surfactant developed at present is difficult to be provided simultaneously with salt-resistance and temperature tolerance both characteristics, Its application in terms of oil exploitation is constrained to a certain extent.
The content of the invention
It is difficult to be provided simultaneously with the technical problems such as salt-resistance and temperature tolerance to solve existing surfactant, mesh of the invention Be a kind of polyoxyethylene sulfonic acid salt form Gemini surface active agent and preparation method thereof is provided.The raw material that this method is related to is easy , reaction condition is gentle, and technique is simple, and the polyoxyethylene sulfonic acid salt form Gemini surface active agent purity being prepared is high, yield Height, there are the physicochemical properties such as good salt-resistance and heat-resisting quantity.
The purpose of the present invention is achieved by the following technical programs：
The present invention provides a kind of polyoxyethylene sulfonic acid salt form Gemini surface active agent, the polyoxyethylene sulfonic acid salt form Shuangzi table The structural formula of face activating agent is shown in formula I：
Wherein：N values are 6,7,8,9,10,12 or 14；M values are 4,5,6,7,8,9,10,15 or 20.
In above-mentioned polyoxyethylene sulfonic acid salt form Gemini surface active agent, it is preferable that the polyoxyethylene sulfonic acid salt form Shuangzi table The one kind of face activating agent in following structural formula：
The present invention also provides the preparation method of above-mentioned polyoxyethylene sulfonic acid salt form Gemini surface active agent, and it includes following step Suddenly：
Step 1, alkylphenol and formaldehyde are subjected to electrophilic substitution reaction generation bigeminy alkylphenol；
Step 2, by bigeminy alkylphenol and oxirane under nitrogen protection, using potassium hydroxide as catalyst, progress Ring-opening reaction generates bigeminy polyethenoxy alkylphenols；
Step 3, by bigeminy polyethenoxy alkylphenols and propane sulphur lactones in the presence of metallic sodium, in organic molten Reaction generation polyoxyethylene sulfonic acid salt form Gemini surface active agent in agent；
Wherein：The mol ratio of the alkylphenol and the formaldehyde is (1-4)：1；The bigeminy alkylphenol and the ring The mol ratio of oxidative ethane is 1：(8-40)；The mol ratio of the bigeminy polyethenoxy alkylphenols and the propane sulphur lactones is 1：(2-8)；The dosage of the potassium hydroxide is the 0.1wt%-0.2wt% of the alkylphenol dosage；The bigeminy polyoxy second The mol ratio of allylic alkylation phenol ether and the metallic sodium is 1：2.
In above-mentioned preparation method, it is preferable that in step 1, the alkylphenol and formaldehyde progress parental materials are anti- Should be carried out in the sour environment of two oxalic acid hydrates, the pH value of sour environment is 3-5.
In above-mentioned preparation method, it is preferable that in step 1, the alkylphenol and formaldehyde progress parental materials are anti- During answering, neopelex is also added into, its dosage is the 0.5wt%-1.0wt% of alkylphenol dosage；This ten Dialkyl benzene sulfonic acids sodium can play a part of reducing interface energy as surfactant.
In above-mentioned preparation method, it is preferable that the alkylphenol include to hexylphenol, to heptylphenol, to octyl group benzene Phenol, nonylphenol, to decyl phenol, to dodecyl phenol and to one or more combinations in myristyl phenol.
In above-mentioned preparation method, it is preferable that in step 1, the alkylphenol and formaldehyde progress parental materials are anti- The reaction temperature answered is 90-150 DEG C, reaction time 4-8h.
In above-mentioned preparation method, it is preferable that in step 2, the bigeminy alkylphenol and oxirane progress open loop are anti- The reaction temperature answered is 150-200 DEG C, reaction pressure 0.1MPa-0.5MPa, reaction time 2-4h.
In above-mentioned preparation method, it is preferable that in step 3, the bigeminy polyoxyethylene alkylphenols and the propane sulphur Reaction temperature when lactones is reacted is 80-120 DEG C, reaction time 24-48h.
In above-mentioned preparation method, it is preferable that in step 3, the organic solvent includes tetrahydrofuran, chloroform and dioxy One or more combinations in six rings.
The present invention introduces polyoxyethylene groups on the basis of Gemini surface active and improves its anti-salt property, leads to simultaneously Cross sulfonating reaction introducing sulfonic acid group and improve its heat resistance.
There is the preparation method of polyoxyethylene sulfonic acid salt form Gemini surface active agent provided by the invention raw material to be easy to get, reaction Mild condition, preparation technology is simple, the polyoxyethylene sulfonic acid salt form Gemini surface active agent rate being prepared, purity 95% with On, yield more than 88%.With physicochemical properties such as good salt-resistances and heat-resisting quantity, apply in high temperature, high salinity Oil recovery factor can be effectively improved in exploitation Deng Complex Reservoir, is had broad application prospects in field of petroleum exploitation.
Brief description of the drawings
Polyoxyethylene sulfonic acid salt form Gemini surface active agent PSS-m when Fig. 1 is 25 DEG C in the embodiment of the present invention 5 (m=10, 15,20, n=9) aqueous solution surface tension and concentration relationship figure；
Fig. 2 is polyoxyethylene sulfonic acid salt form Gemini surface active agent PSS-m (m=10,15,20, n in the embodiment of the present invention 5 =9) aqueous solution surface tension and Na+Concentration relationship figure.
Embodiment
In order to which technical characteristic, purpose and the beneficial effect of the present invention is more clearly understood, now to the skill of the present invention Art scheme carry out it is described further below, but it is not intended that to the present invention can practical range restriction.
Embodiment 1
The present embodiment provides a kind of polyoxyethylene sulfonic acid salt form Gemini surface active agent, the polyoxyethylene sulfonic acid salt form Shuangzi Shown in the structural formula of surfactant such as formula (1)：
The present embodiment also provides the preparation method of above-mentioned polyoxyethylene sulfonic acid salt form Gemini surface active agent, and it includes following Step：
(1) preparation of bigeminy nonyl phenol：By nonylphenol and formaldehyde according to mol ratio 2：1 ratio weighs, to burning 0.495g two oxalic acid hydrates, 0.325g deionized waters and 0.185g dodecyls are added in bottle after addition nonylphenol Benzene sulfonic acid sodium salt, solid formaldehyde is added portionwise during being warming up to 90 DEG C and is uniformly mixed, then be warming up to 120 DEG C, connect a point water Device, react 4h.React and extract product with dichloromethane after terminating, then revolving is dried, then column chromatography purified product (silica gel Post：Ethyl acetate-light petrol elutes system), as bigeminy nonyl phenol.
(2) preparation of bigeminy polyoxyethylene nonylphenol ether：By bigeminy nonyl phenol and oxirane in molar ratio 1：40 Ratio weigh, bigeminy nonyl phenol and potassium hydroxide catalyst (dosage is the 0.1wt% of nonylphenol) are added to anti- Answer in kettle, vacuumize and replace nitrogen three times, be passed through nitrogen protection, be passed through oxirane with nitrogen under the conditions of anhydrous and oxygen-free 0.15MPa pressure is maintained into reactor and oxyethylation addition reaction is carried out under the conditions of 170 DEG C until oxirane adds Untill, 60 DEG C are cooled to, then with acetic acid or phosphoric acid neutralization reaction product and is post-processed, obtains bigeminy ethylene nonyl Phenol ether.
(3) preparation of polyoxyethylene sulfonic acid salt form Gemini surface active agent：By 48.6g bigeminy polyoxyethylene nonylphenol ethers 4 hours (mol ratio, sodium are reacted in tetrahydrofuran with 2.3g metallic sodiums：Bigeminy polyoxyethylene nonylphenol=2：1), Ran Houjia Enter propane sultone (in molar ratio, propane sultone：Bigeminy polyoxyethylene nonylphenol ether=2：1), maintenance reaction temperature exists 90 DEG C, 24h is reacted, removes solvent, acetone ether mixed liquor is then added and recrystallizes to obtain the present embodiment polyoxyethylene sulfonic acid salt form Gemini surface active agent.The yield of the polyoxyethylene sulfonic acid salt form Gemini surface active agent is 88%, purity 95%.
The polyoxyethylene sulfonic acid salt form Gemini surface active agent that the present embodiment is prepared carries out nmr analysis, nuclear-magnetism point It is as follows to analyse result：1H NMR(CDCl3, 400MHz), δ 7.19 (d, 4H, 2ArH), 7.05 (t, 4H, 2ArH), 6.80 (d, 4H, 2ArH), 4.11 (t, 4H, 2CH2), 3.62-3.83 (m, 156H, CH2-CH2- O), 3.37 (t, 4H, 2CH2), 2.55 (m, 4H, 2CH2),2.02(m,4H,2CH2),1.66–0.54(m,38H,2C9H19), the preparation is shown by the parsing of nuclear magnetic resonance spectroscopy result Polyoxyethylene sulfonic acid salt form Gemini surface active agent prepared by method is structure above.
Embodiment 2
The present embodiment provides a kind of polyoxyethylene sulfonic acid salt form Gemini surface active agent, the polyoxyethylene sulfonic acid salt form Shuangzi Shown in the structural formula of surfactant such as formula (2)：
The present embodiment also provides the preparation method of above-mentioned polyoxyethylene sulfonic acid salt form Gemini surface active agent, and it includes following Step：
(1) preparation of bigeminy heptylphenol：Will be to heptylphenol and formaldehyde according to mol ratio 2.5：1 ratio weighs, to Add two oxalic acid hydrates to adding 0.512g after heptylphenol in flask, the 12 of 0.345g deionized waters and 0.185g Sodium alkyl benzene sulfonate, solid formaldehyde is added portionwise during being warming up to 90 DEG C and is uniformly mixed, then be warming up to 120 DEG C, connect Water knockout drum, react 6h.React and extract product with dichloromethane after terminating, then dried and rotated with anhydrous magnesium sulfate, then column chromatography Purified product (silicagel column：Ethyl acetate-light petrol elutes system), as bigeminy heptylphenol.
(2) preparation of bigeminy polyoxyethylene heptyl benzene phenolic ether：By bigeminy heptylphenol and oxirane in molar ratio 1：30 Ratio weigh, bigeminy heptylphenol and potassium hydroxide catalyst (dosage is the 0.2wt% to heptylphenol) are added to anti- Answer in kettle, vacuumize and replace nitrogen three times, be passed through nitrogen protection, be passed through oxirane with nitrogen under the conditions of anhydrous and oxygen-free Into reactor maintain 0.2MPa pressure and under the conditions of 180 DEG C carry out oxyethylation addition reaction until oxirane add for Only, 60 DEG C are cooled to, then with acetic acid or phosphoric acid neutralization reaction product and is post-processed, obtains bigeminy polyethylene heptylphenol Ether.
(3) preparation of polyoxyethylene sulfonic acid salt form Gemini surface active agent：By 36.6g bigeminy polyethylene heptyl benzene phenolic ether with 18.3g propane sulphurs lactones weighs mixing, adds 50ml tetrahydrofurans as solvent, adds 2.3g metallic sodiums and make catalyst, tie up Reaction temperature is held at 95 DEG C, reacts 24h, removes solvent, acetone ether mixed liquor is then added and recrystallizes to obtain the present embodiment polyoxy Vinyl sulfonic acid salt form Gemini surface active agent；The yield of the polyoxyethylene sulfonic acid salt form Gemini surface active agent is 88%, purity 96%.
The polyoxyethylene sulfonic acid salt form Gemini surface active agent that the present embodiment is prepared carries out nmr analysis, nuclear-magnetism point It is as follows to analyse result：1H NMR(CDCl3, 400MHz), δ 7.19 (d, 4H, 2ArH), 7.05 (t, 4H, 2ArH), 6.80 (d, 4H, 2ArH), 4.11 (t, 4H, 2CH2), 3.62-3.83 (m, 116H, CH2-CH2- O), 3.32 (t, 4H, 2CH2), 2.55 (m, 4H, 2CH2),2.00(m,4H,2CH2),1.66–0.54(m,30H,2C7H15) by nuclear magnetic resonance spectroscopy result parsing show the preparation side Polyoxyethylene sulfonic acid salt form Gemini surface active agent prepared by method is structure above.
Embodiment 3
The present embodiment provides a kind of polyoxyethylene sulfonic acid salt form Gemini surface active agent, the polyoxyethylene sulfonic acid salt form Shuangzi Shown in the structural formula of surfactant such as formula (3)：
The present embodiment also provides the preparation method of above-mentioned polyoxyethylene sulfonic acid salt form Gemini surface active agent, and it includes following Step：
(1) preparation of bigeminy dodecyl phenol：Will be to dodecyl phenol and formaldehyde according to mol ratio 2.2：1 ratio Weigh, add two oxalic acid hydrates to adding 0.48g after dodecyl phenol into flask, 0.33g deionized waters and 0.17g neopelex, solid formaldehyde is added portionwise during being warming up to 90 DEG C and is uniformly mixed, then be warming up to 120 DEG C, water knockout drum is connected, reacts 5h.React and extract product with dichloromethane after terminating, then dried and rotated with anhydrous magnesium sulfate, Then column chromatography purified product, bigeminy dodecyl phenol is obtained.
(2) preparation of bigeminy polyoxyethylene lauryl alkylphenol ether：Bigeminy dodecyl phenol and oxirane are massaged That ratio 1：18 ratio weighs, and by bigeminy dodecyl phenol and potassium hydroxide catalyst, (dosage is to dodecyl phenol 0.2wt%) it is added in reactor, vacuumizes and replace nitrogen three times, nitrogen protection is passed through, by ring under the conditions of anhydrous and oxygen-free Oxidative ethane is passed into reactor with nitrogen to be maintained 0.25MPa pressure and carries out under the conditions of 190 DEG C oxyethylation addition reaction Untill oxirane adds, 60 DEG C are cooled to, then with acetic acid or phosphoric acid neutralization reaction product and is post-processed, obtained Bigeminy polyoxyethylene lauryl alkylphenol ether.
(3) preparation of polyoxyethylene sulfonic acid salt form Gemini surface active agent：Weigh previous step product 51.6g and 15.25g third Alkane sulphur lactones weighs mixing, adds 50ml tetrahydrofurans as solvent, 2.3g metallic sodiums make catalyst, and maintenance reaction temperature exists 90 DEG C, 24h is reacted, removes solvent, acetone ether mixed liquor is then added and recrystallizes to obtain the present embodiment polyoxyethylene sulfonic acid salt form Gemini surface active agent；The yield of the polyoxyethylene sulfonic acid salt form Gemini surface active agent is 90%；Purity 95%.
The polyoxyethylene sulfonic acid salt form Gemini surface active agent that the present embodiment is prepared carries out nmr analysis, nuclear-magnetism point It is as follows to analyse result：1H NMR(CDCl3, 400MHz), δ 7.19 (d, 4H, 2ArH), 7.05 (t, 4H, 2ArH), 6.80 (d, 4H, 2ArH), 4.11 (t, 4H, 2CH2), 3.64-3.92 (m, 76H, CH2-CH2- O), 3.30 (t, 4H, 2CH2), 2.58 (m, 4H, 2CH2),2.08(m,4H,2CH2),1.66–0.54(m,50H,2C12H25), the preparation is shown by the parsing of nuclear magnetic resonance spectroscopy result Polyoxyethylene sulfonic acid salt form Gemini surface active agent prepared by method is structure above.
Embodiment 4
The present embodiment provides a kind of polyoxyethylene sulfonic acid salt form Gemini surface active agent, the polyoxyethylene sulfonic acid salt form Shuangzi Shown in the structural formula of surfactant such as formula (4)：
The present embodiment also provides the preparation method of above-mentioned polyoxyethylene sulfonic acid salt form Gemini surface active agent, and it includes following Step：
(1) preparation of bigeminy decyl phenol：Will be to decyl phenol and formaldehyde according to mol ratio 2.4：1 ratio weighs, to The dodecane of two oxalic acid hydrates to adding 0.51g after decyl phenol, 0.35g deionized waters and 0.18g is added in flask Base benzene sulfonic acid sodium salt, solid formaldehyde is added portionwise during being warming up to 90 DEG C and is uniformly mixed, then be warming up to 120 DEG C, connect point Hydrophone, react 5h.React and extract product with dichloromethane after terminating, then dried and rotated with anhydrous magnesium sulfate, then column chromatography carries Pure products, obtain bigeminy decyl phenol.
(2) preparation of bigeminy polyoxyethylene decyl phenol ether：By bigeminy decyl phenol and oxirane in molar ratio 1：10 Ratio weigh, bigeminy decyl phenol and potassium hydroxide catalyst (dosage is the 0.1wt% to decyl phenol) are added to anti- Answer in kettle, vacuumize and replace nitrogen three times, be passed through nitrogen protection, be passed through oxirane with nitrogen under the conditions of anhydrous and oxygen-free Into reactor maintain 0.3MPa pressure and under the conditions of 200 DEG C carry out oxyethylation addition reaction until oxirane add for Only, 60 DEG C are cooled to, then with acetic acid or phosphoric acid neutralization reaction product and is post-processed, obtains bigeminy polyoxyethylene decyl benzene Phenolic ether.
(3) preparation of polyethenoxy alkylphenols sulphonate type gemini surfactant：By 84.6g bigeminy polyoxyethylene Decyl phenol ether mixes with 14.64g propane sulphur lactones, adds 60mL tetrahydrofurans and is catalyzed as solvent, 2.3g metallic sodiums Agent, maintenance reaction temperature react 24h at 90 DEG C, remove solvent, then add acetone ether mixed liquor and recrystallize to obtain the present embodiment Polyoxyethylene sulfonic acid salt form Gemini surface active agent；The yield of the polyoxyethylene sulfonic acid salt form Gemini surface active agent is 92%； Purity 96%.
The polyoxyethylene sulfonic acid salt form Gemini surface active agent that the present embodiment is prepared carries out nmr analysis, nuclear-magnetism point It is as follows to analyse result：1H NMR(CDCl3, 400MHz), δ 7.19 (d, 4H, 2ArH), 7.05 (t, 4H, 2ArH), 6.80 (d, 4H, 2ArH), 4.11 (t, 4H, 2CH2), 3.68-3.88 (m, 36H, CH2-CH2- O), 3.38 (t, 4H, 2CH2), 2.52 (m, 4H, 2CH2),2.02(m,4H,2CH2),1.66–0.54(m,42H,2C10H21), the preparation is shown by the parsing of nuclear magnetic resonance spectroscopy result Polyoxyethylene sulfonic acid salt form Gemini surface active agent prepared by method is structure above.
Embodiment 5
The present embodiment provides polyoxyethylene sulfonic acid salt form Gemini surface active agent anti-salt temperature-resistant performance test experiment of the present invention. Experimental result as shown in Figure 1, Figure 2 with shown in table 1, polyoxyethylene sulfonic acid salt form Gemini surface active agent PSS-m (m when Fig. 1 shows 25 DEG C =10,15,20, n=9) aqueous solution surface tension and concentration relationship figure；Fig. 2 shows that polyoxyethylene sulfonic acid salt form Shuangzi surface is lived Property agent PSS-m (m=10,15,20, n=9) aqueous solution surface tension and Na+ concentration relationship figures.Table 1 shows polyoxyethylene sulfonic acid Salt form Gemini surface active agent PSS-m (m=10,15,20, n=9) cloud point.
Table 1
PSS-m cloud point (DEG C)
M=10 >100
M=15 >100
M=20 >100
From experimental data, the polyoxyethylene sulfonic acid salt form Gemini surface active agent that the present invention is prepared has good There is excellent salt-resistance and heat-resisting quantity.
In summary, the preparation method of polyoxyethylene sulfonic acid salt form Gemini surface active agent provided by the invention has raw material It is easy to get, reaction condition is gentle, and preparation technology is simple, the polyoxyethylene sulfonic acid salt form Gemini surface active agent rate being prepared, pure Degree more than 95%, yield more than 88%.With physicochemical properties such as good salt-resistances and heat-resisting quantity, apply high temperature, Oil recovery factor can be effectively improved in the exploitation of the Complex Reservoirs such as high salinity, before there is wide application in field of petroleum exploitation Scape.

Claims (10)

  1. A kind of 1. polyoxyethylene sulfonic acid salt form Gemini surface active agent, it is characterised in that the polyoxyethylene sulfonic acid salt form Shuangzi table The structural formula of face activating agent is shown in formula I：
    Wherein：N values are 6,7,8,9,10,12 or 14；M values are 4,5,6,7,8,9,10,15 or 20.
  2. 2. polyoxyethylene sulfonic acid salt form Gemini surface active agent according to claim 1, it is characterised in that the polyoxyethylene The one kind of sulphonate type gemini surfactant in following structural formula：
  3. 3. the preparation method of the polyoxyethylene sulfonic acid salt form Gemini surface active agent described in claim 1, it comprises the following steps：
    Step 1, alkylphenol and formaldehyde are subjected to electrophilic substitution reaction generation bigeminy alkylphenol；
    Step 2, by bigeminy alkylphenol and oxirane under nitrogen protection, using potassium hydroxide as catalyst, progress open loop Reaction generation bigeminy polyethenoxy alkylphenols；
    Step 3, by bigeminy polyethenoxy alkylphenols and propane sultone in the presence of metallic sodium, in organic solvent Reaction generation polyoxyethylene sulfonic acid salt form Gemini surface active agent；
    Wherein：The mol ratio of the alkylphenol and the formaldehyde is (1-4)：1；The bigeminy alkylphenol and the epoxy second The mol ratio of alkane is 1：(8-40)；The mol ratio of the bigeminy polyethenoxy alkylphenols and the propane sultone is 1： (2-8)；The dosage of the potassium hydroxide is the 0.1wt%-0.2wt% of the alkylphenol dosage；The bigeminy polyoxyethylene The mol ratio of alkylbenzene phenolic ether and the metallic sodium is 1：2.
  4. 4. preparation method according to claim 3, it is characterised in that：In step 1, the alkylphenol and the first Aldehyde, which carries out electrophilic substitution reaction, to be carried out in the sour environment of two oxalic acid hydrates, and the pH value of sour environment is 3-5.
  5. 5. preparation method according to claim 3, it is characterised in that：In step 1, the alkylphenol and the first During aldehyde carries out electrophilic substitution reaction, neopelex is also added into, its dosage is alkylphenol dosage 0.5wt%-1.0wt%.
  6. 6. preparation method according to claim 3, it is characterised in that：The alkylphenol is included to hexylphenol, to heptan Base phenol, POP, nonylphenol, to decyl phenol, to dodecyl phenol and to one in myristyl phenol Kind or a variety of combinations.
  7. 7. according to the preparation method described in claim any one of 3-5, it is characterised in that：In step 1, the alkylphenol The reaction temperature that electrophilic substitution reaction is carried out with the formaldehyde is 90-150 DEG C, reaction time 4-8h.
  8. 8. preparation method according to claim 3, it is characterised in that：In step 2, the bigeminy alkylphenol and ring The reaction temperature that oxidative ethane carries out ring-opening reaction is 150-200 DEG C, reaction pressure 0.1MPa-0.5MPa, reaction time 2- 4h。
  9. 9. preparation method according to claim 3, it is characterised in that：In step 3, the bigeminy is polyxyethylated Reaction temperature when phenol is reacted with the propane sulphur lactones is 80-120 DEG C, reaction time 24-48h.
  10. 10. preparation method according to claim 3, it is characterised in that：In step 3, the organic solvent includes tetrahydrochysene One or more combinations in furans, chloroform and dioxane.
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CN108285781A (en) * 2018-03-19 2018-07-17 青岛大学 A kind of high contents of calcium and magnesium oil reservoir complexed surfactant oil displacement system
WO2022099826A1 (en) * 2020-11-16 2022-05-19 山东大明精细化工有限公司 Gemini polyoxyethylene ether succinate surfactant for oil displacement and preparation method therefor

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