CN102584641A - Process for preparing alkylphenol formaldehyde oligomer sulfonate - Google Patents
Process for preparing alkylphenol formaldehyde oligomer sulfonate Download PDFInfo
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Abstract
The invention discloses a process for preparing alkylphenol formaldehyde oligomer sulfonate. The process comprises the following steps of: adding alkylphenol and a catalyst into a reaction kettle, heating with stirring, dripping a formaldehyde solution or paraformaldehyde, continuously stirring, and raising temperature to reaction temperature, adding residual formaldehyde solution or paraformaldehyde, continuously reacting, and after reaction is finished, adding a sodium hydroxide aqueous solution to adjust pH of a reaction product to be 6.5 to 8.0 to obtain alkylphenol formaldehyde oligomer; and adding the alkylphenol formaldehyde oligomer into the reaction kettle, adding a solvent to dissolve, opening a stirrer, stirring and heating to 30 to 80 DEG C, adding a sulfonating agent, continuously reacting for 30 to 90 minutes, neutralizing a sulfonating product by using alkali until pH is 7 to 8, and evaporating to remove the solvent to obtain the alkylphenol formaldehyde oligomer sulfonate. The process has the advantages that alkylphenol and formaldehyde are used as raw materials, the process is simple, and industrialization is easy to realize.
Description
Technical field
The present invention relates to a kind of technology for preparing alkylphenol formaldehyde oligopolymer sulphonate with alkylphenol and formolite reaction.
Background technology
Oligomeric-type tensio-active agent (oligomeric surfactant) is that the common strand surfactant molecule more than 2 or 2 is connected together through chamical binding with spacer group (spacer group) at hydrophilic group or near near hydrophilic group.Have simultaneously in the molecule amphiphilic compositions such as 2,3 or 4 be called as dimerization (dimeric) respectively, trimerization (trimeric), four gathers oligomeric-type tensio-active agents such as (tetrameric).Compare with conventional surfactant, gathering behavior and more excellent character that the oligomeric-type tensio-active agent has lower micelle-forming concentration, enriches more especially have certain application potential aspect TOR.
At present; Research to oligo surfactant both at home and abroad mainly concentrates on dimeric surfactant; The trimerization that the polymerization degree is high slightly, four gathers, five tensio-active agent such as gather research mainly concentrate on positively charged ion or non-ionics, and relevant trimerization, four gathers, five the rarely seen report of AS such as gather.For example: Laschewsky, Argentine Grau and China Chinese Academy of Sciences chemistry institute of the Esumi of the Zana of France, the Menger of the U.S., Japan and Ikeda, Germany, chemical institute of University of Fuzhou, department of chemistry of institute of college of science of University Of Tianjin, chemical engineering institute of Hebei University of Technology etc. have all carried out preliminary research to the oligomeric-type tensio-active agent.But above research biases toward the synthetic and performance applications of laboratory lab scale mostly, raw material be difficult to obtain or cost too high, synthesis step is too complicated, industrialized feasibility is little.
Alkylphenol formaldehyde oligopolymer sulphonate is by the condensation of alkylphenol, formaldehyde elder generation, carries out the oligomeric-type sulfonate anionic surfactant that obtains after the sulfonation with sulphonating agent again.Raw material sources are abundant, and cost is low, and compound method is simple relatively, is easy to realize industriallization.At present, after only Zheng of University Of Tianjin Bao Jiang reacts with mol ratio with NP and formaldehyde at 2: 1, use the chlorsulfonic acid sulfonation, obtain sulfonate dimer, i.e. two (2-hydroxyl-3-sodium sulfonate group-5-nonyl phenyl) methane.By alkylphenol, formaldehyde is that the report that raw material synthetic trimerization, four such as gathers at sulfosalt surfactant is not seen as yet.
Undertaken by alkylphenol and formaldehyde in the process of polycondensation synthesis of oligonucleotides thing midbody, the kind of catalyzer and consumption are very important to the influence of the alkylphenol transformation efficiency and the polymerization degree.US3919429 proposes to make alkylphenol and formaldehyde condensation polymer catalyst for reaction with hydrochloric acid, sulfuric acid, phosphoric acid and oxalic acid, and it is 1～9 alkylphenol formaldehyde polycondensate that the dependence distillation dehydration obtains the polymerization degree.CN200510126038.4 proposes to make the synthetic NP formaldehyde trimerization midbody of catalyzer with Pottasium Hydroxide.CN200810152433.3 is the synthetic NP formaldehyde trimerization midbody that obtains of catalyzer with the solid super-strong acid.Hebei University of Technology chemistry and the Li Gang of chemical engineering institute equal to utilize NP, formaldehyde to be raw material in 2010, have obtained NP formaldehyde dimer or tripolymer with oxalic acid or solid super-strong acid as Preparation of Catalyst respectively.
To sum up, there is following problem in the preparation technology of existing alkylphenol formaldehyde oligopolymer:
1. for basic catalyst such as Pottasium Hydroxide, NP and formolite reaction are prone to form the end capped oligopolymer of methylol, are not the midbodys that this problem is expected, alkali corrosion equipment in addition, contaminate environment.
2. when making catalyzer as with hydrochloric acid, NP and formolite reaction are violent, the easy formation of hydrochloric acid and formaldehyde monochloromethyl-ether by product in the reaction process, and this material is considered to the potential carcinogens.As making catalyzer with sulfuric acid, because of its dehydration property is too strong, make polycondensate intramolecular dehydration and loss of activity-OH group, thus the ability of forfeiture crosslinking reaction.In addition, all there is etching apparatus in inorganic acid catalysts such as hydrochloric acid, sulfuric acid, the defective of contaminate environment.
3. for organic acid catalyst such as oxalic acid, because of its acidity a little less than, so NP and formolite reaction gentle, last long, energy consumption is big.
4. for solid acid catalyst, it prepares process need high-temperature calcination, time consumption and energy consumption.
5. above-mentioned report all is to reduce pressure after the first polycondensation to dewater, and process step is more, and facility investment is big, long reaction time, and yield is lower.The mode that employing vacuumizes is removed solvent and water, and system viscosity increases, the aftertreatment trouble.
Summary of the invention
The purpose of this invention is to provide a kind of is the technology that raw material, technology are simple, be easy to industrialized preparation alkylphenol formaldehyde oligopolymer sulphonate with alkylphenol and formaldehyde.
The present invention is in the presence of an acidic catalyst; Alkylphenol and formaldehyde generation polycondensation; Obtain by methylene radical alkylphenol at-linear alkyl phenol formaldehyde oligomer (structural formula is seen formula 1) that the OH ortho position links up; With sulphonating agent the alkylphenol formaldehyde oligopolymer is carried out sulfonation then, thereby make alkylphenol formaldehyde oligopolymer sulphonate.
The present invention is a kind of technology for preparing alkylphenol formaldehyde oligopolymer sulphonate, and the concrete operations step is following:
(1) preparation alkylphenol formaldehyde oligopolymer
In reaction kettle, add alkylphenol, catalyzer; Catalyst levels is 0.1%～10.0% of an alkylphenol quality; Under agitation condition and after being heated to 30～50 ℃, drip 50%～80% of formaldehyde solution or the total sample introduction quality of Paraformaldehyde 96, continue to stir and add remaining formaldehyde solution or Paraformaldehyde 96 again after being warming up to 60～120 ℃ of temperature of reaction; The mol ratio of alkylphenol and formaldehyde or Paraformaldehyde 96 is 1: 0.5～5; Under this temperature of reaction, continue reaction 30～240min, reaction finishes the back with adding aqueous sodium hydroxide solution conditioned reaction product to PH=6.5～8.0, obtains the alkylphenol formaldehyde oligopolymer;
(2) preparation alkylphenol formaldehyde oligopolymer sulphonate
In reaction kettle, add the alkylphenol formaldehyde oligopolymer; After adding dissolution with solvents; Add sulphonating agent when unlatching is heated with stirring to 30～80 ℃, the mol ratio of sulphonating agent and alkylphenol formaldehyde oligopolymer is 10～1: 1, adds continued reaction 30～90min; It is 7～8 that sulfonated products uses alkali to be neutralized to pH, obtains alkylphenol formaldehyde oligopolymer sulphonate after steaming desolventizes.
Aforesaid alkylphenol R
1-OH, R
1Be C
8～C
24Straight chain, branched-chain alkyl phenol, or the mixed phenol of different alkane chains etc.
Aforesaid catalyzer can be an alkyl aryl sulphonic acid, also can be alkylsulphonic acid etc.
Aforesaid alkyl aryl sulphonic acid R
2-Ar-SO
3H, R2 are C
1～C
16Straight chain, branched-chain alkyl aryl sulfonic acid, or different alkane chain blended alkyl aryl sulphonic acids etc., Ar is phenyl, naphthyl, phenylbenzene etc.
Aforesaid alkylsulphonic acid R
3-SO
3H, R
3Be C
8～C
24Straight chain, branched-chain alkyl sulfonic acid, or different alkane chain blended alkylsulphonic acids etc.
Aforesaid solvent can be C
6～C
20Alkane (comprising normal paraffin, isoparaffin, branched paraffin, naphthenic hydrocarbon), halohydrocarbon (comprising methylene dichloride, ethylene dichloride, trichloromethane) etc.
Aforesaid sulphonating agent can be oleum, sulfan, gas sulphur trioxide etc.
Aforesaid sulfan can be dissolved in halohydrocarbon (comprising methylene dichloride, ethylene dichloride) and add in the reaction kettle again, also can directly add.
Aforesaid gas sulphur trioxide can be the sulphur trioxide/air gas mixture that is obtained by combustion sulphur method, oleum acid gas formulation, sulfur dioxide liquid catforming or sulfan direct boiling method.
In aforesaid sulphur trioxide/air gas mixture, the volume(tric)fraction of sulphur trioxide is in 5～20% scopes.
Aforesaid alkali used in sulfonation process can be mineral alkali, comprises sodium hydroxide, Pottasium Hydroxide etc.; Can be organic bases also, comprise ammoniacal liquor, monoethanolamine, diethylolamine, trolamine, tetra-allkylammonium etc.
Aforesaid polycondensation or sulfonation reaction device all have whisking appliance, prolong, TM etc.
The technology that the present invention prepares alkylphenol formaldehyde oligopolymer sulphonate has the following advantages:
(1) preparation alkylphenol formaldehyde oligopolymer sulphonate technology of the present invention can obtain the suitable oligomeric-type tensio-active agent of the polymerization degree, and easy to operate, technology is simple.
(2) preparation alkylphenol formaldehyde oligopolymer midbody technology of the present invention has been removed solvent; Not obvious to the influence of alkylphenol transformation efficiency on the one hand, save underpressure distillation on the other hand and removed solvent, simplified post-treating method; Help energy-conservationly, shorten the operational cycle.
(3) the catalyzer alkyl aryl sulphonic acid itself has dispersiveness in the preparation alkylphenol formaldehyde oligopolymer midbody technology of the present invention, and alkylphenol is fully contacted with formaldehyde solution, has improved catalytic activity.
(4) the alkylphenol formaldehyde oligopolymer sulphonate of the present invention preparation has performances such as surfactivity height, foam ability are strong, high temperature resistant, is highly suitable for preparing the TOR oil-displacing agent.
Embodiment
Embodiment 1: in the reaction kettle that has TM, whisking appliance, prolong, add C
8Straight chained alkyl phenol, catalyzer straight chain Witco 1298 Soft Acid; Catalyst levels is 0.1% of an alkylphenol quality; After open stirring and being heated to 30 ℃, drip 50% of the total sample introduction quality of formaldehyde, continue to stir and add remaining formaldehyde again after being warming up to 60 ℃ of temperature of reaction; The mol ratio of alkylphenol and formaldehyde is 1: 0.5, under this temperature of reaction, continues reaction 240min.Reaction finish the back use add aqueous sodium hydroxide solution conditioned reaction product to PH be 7.5, obtain the tawny gelatinoid at last, i.e. the alkylphenol formaldehyde oligopolymer.
In the reaction kettle that has TM, whisking appliance, prolong, add the alkylphenol formaldehyde oligopolymer, after the dissolving of adding octane-iso, open an amount of oleum of adding when being heated with stirring to 30 ℃, the SO in the oleum
3With the mol ratio of alkylphenol formaldehyde oligopolymer be 10: 1, add continued reaction 90min, it is 7 that sulfonated products uses the KOH aqueous solution to be neutralized to pH, steams to obtain alkylphenol formaldehyde oligopolymer sulphonate after desolventizing.
Embodiment 2: in the reaction kettle that has TM, whisking appliance, prolong, add C
9Branched-chain alkyl phenol, catalyzer tosic acid; Catalyst levels is 10.0% of an alkylphenol quality; After open stirring and being heated to 50 ℃, drip 60% of the total sample introduction quality of Paraformaldehyde 96, continue to stir and add remaining Paraformaldehyde 96 again after being warming up to 120 ℃ of temperature of reaction; The mol ratio of the formaldehyde in alkylphenol and the Paraformaldehyde 96 is 1: 5, under this temperature of reaction, continues reaction 30min.Reaction finish the back use add aqueous sodium hydroxide solution conditioned reaction product to PH be 6.5, obtain the tawny gelatinoid at last, i.e. the alkylphenol formaldehyde oligopolymer.
In the reaction kettle that has TM, whisking appliance, prolong, add the alkylphenol formaldehyde oligopolymer, after the dissolving of adding cyclohexane, open when being heated with stirring to 80 ℃, add an amount of sulphonating agent liquid SO
3, SO
3With the mol ratio of alkylphenol formaldehyde oligopolymer be 1: 1, add continued reaction 90min, it is 7.5 that sulfonated products uses monoethanolamine to be neutralized to pH, steams to obtain alkylphenol formaldehyde oligopolymer sulphonate after desolventizing.
Embodiment 3: in the reaction kettle that has TM, whisking appliance, prolong, add C
12Branched-chain alkyl phenol, catalyzer isobutyl-naphthene sulfonic acid; Catalyst levels is 5.0% of an alkylphenol quality; After open stirring and being heated to 40 ℃, drip 80% of the total sample introduction quality of formaldehyde, continue to stir and add remaining formaldehyde again after being warming up to 80 ℃ of temperature of reaction; The mol ratio of alkylphenol and formaldehyde is 1: 1.5, under this temperature of reaction, continues reaction 90min.Reaction finish the back use add aqueous sodium hydroxide solution conditioned reaction product to PH be 7.3, obtain the tawny gelatinoid at last, i.e. the alkylphenol formaldehyde oligopolymer.
In the reaction kettle that has TM, whisking appliance, prolong, add the alkylphenol formaldehyde oligopolymer, after the dissolving of adding methylene dichloride, unlatching adds an amount of liquid SO again when being heated with stirring to 50 ℃
3/ ethylene dichloride mixture, SO
3With the mol ratio of alkylphenol formaldehyde oligopolymer be 3: 1, add continued reaction 40min, it is 8 that sulfonated products uses trolamine to be neutralized to pH, steams to obtain alkylphenol formaldehyde oligopolymer sulphonate after desolventizing.
Embodiment 4: in the reaction kettle that has TM, whisking appliance, prolong, add C
18Straight chained alkyl phenol, catalyzer side chain C24 alkylsulphonic acid; Catalyst levels is 2.5% of an alkylphenol quality; After open stirring and being heated to 50 ℃, drip 75% of the total sample introduction quality of formaldehyde, continue to stir and add remaining formaldehyde again after being warming up to 70 ℃ of temperature of reaction; The mol ratio of alkylphenol and formaldehyde is 1: 3, under this temperature of reaction, continues reaction 120min.Reaction finish the back use add aqueous sodium hydroxide solution conditioned reaction product to PH be 8.0, obtain the tawny gelatinoid at last, i.e. the alkylphenol formaldehyde oligopolymer.
In the reaction kettle that has TM, whisking appliance, prolong, add the alkylphenol formaldehyde oligopolymer, behind the adding petroleum ether dissolution, open an amount of sulphonating agent SO of adding when being heated with stirring to 40 ℃
3/ air gas mixture, wherein SO
3Volume(tric)fraction be 5%, SO
3With the mol ratio of alkylphenol formaldehyde oligopolymer be 4: 1, add continued reaction 60min, it is 7.7 that sulfonated products uses ammoniacal liquor to be neutralized to pH, steams to obtain alkylphenol formaldehyde oligopolymer sulphonate after desolventizing.
Embodiment 5: in the reaction kettle that has TM, whisking appliance, prolong, add C
24Branched-chain alkyl phenol, catalyzer diethylammonium naphthene sulfonic acid; Catalyst levels is 6.0% of an alkylphenol quality; After open stirring and being heated to 35 ℃, drip 55% of the total sample introduction quality of Paraformaldehyde 96, continue to stir and add remaining Paraformaldehyde 96 again after being warming up to 90 ℃ of temperature of reaction; The mol ratio of the formaldehyde in alkylphenol and the Paraformaldehyde 96 is 1: 4.5, under this temperature of reaction, continues reaction 160min.Reaction finish the back use add aqueous sodium hydroxide solution conditioned reaction product to PH be 6.8, obtain the tawny gelatinoid at last, i.e. the alkylphenol formaldehyde oligopolymer.
In the reaction kettle that has TM, whisking appliance, prolong, add the alkylphenol formaldehyde oligopolymer, after the dissolving of adding trichloromethane, unlatching adds an amount of sulphonating agent liquid SO again when being heated with stirring to 70 ℃
3/ methylene dichloride, SO
3With the mol ratio of alkylphenol formaldehyde oligopolymer be 6: 1, add continued reaction 50min, it is 7.2 that sulfonated products uses the TBuA aqueous solution to be neutralized to pH, steams to obtain alkylphenol formaldehyde oligopolymer sulphonate after desolventizing.
Embodiment 6: in the reaction kettle that has TM, whisking appliance, prolong, add C
14, C
16Straight chained alkyl mixed phenol, catalyzer C
8, C
10Phenylbenzene sulfonic acid; Catalyst levels is 8.0% of an alkylphenol quality; After open stirring and being heated to 45 ℃, drip 60% of the total sample introduction quality of formaldehyde, continue to stir and add remaining formaldehyde again after being warming up to 85 ℃ of temperature of reaction; The mol ratio of alkylphenol and formaldehyde is 1: 1.0, under this temperature of reaction, continues reaction 210min.Reaction finish the back use add aqueous sodium hydroxide solution conditioned reaction product to PH be 7.6, obtain the tawny gelatinoid at last, i.e. the alkylphenol formaldehyde oligopolymer.
In the reaction kettle that has TM, whisking appliance, prolong, add the alkylphenol formaldehyde oligopolymer, after the dissolving of adding ethylene dichloride, open an amount of sulphonating agent SO of adding when being heated with stirring to 50 ℃
3/ air gas mixture, wherein SO
3Volume(tric)fraction be 20%, SO
3With the mol ratio of alkylphenol formaldehyde oligopolymer be 6: 1, add continued reaction 60min, it is 7.5 that sulfonated products uses the NaOH aqueous solution to be neutralized to pH, steams to obtain alkylphenol formaldehyde oligopolymer sulphonate after desolventizing.
Claims (14)
1. a technology for preparing alkylphenol formaldehyde oligopolymer sulphonate is characterized in that comprising the steps:
(1) preparation alkylphenol formaldehyde oligopolymer
In reaction kettle, add alkylphenol, catalyzer; Catalyst levels is 0.1%～10.0% of an alkylphenol quality; Under agitation condition and after being heated to 30～50 ℃, drip 50%～80% of formaldehyde solution or the total sample introduction quality of Paraformaldehyde 96, continue to stir and add remaining formaldehyde solution or Paraformaldehyde 96 again after being warming up to 60～120 ℃ of temperature of reaction; The mol ratio of alkylphenol and formaldehyde or Paraformaldehyde 96 is 1: 0.5～5; Under this temperature of reaction, continue reaction 30～240min, reaction finishes the back with adding aqueous sodium hydroxide solution conditioned reaction product to PH=6.5～8.0, obtains the alkylphenol formaldehyde oligopolymer;
(2) preparation alkylphenol formaldehyde oligopolymer sulphonate
In reaction kettle, add the alkylphenol formaldehyde oligopolymer; After adding dissolution with solvents; Add sulphonating agent when unlatching is heated with stirring to 30～80 ℃, the mol ratio of sulphonating agent and alkylphenol formaldehyde oligopolymer is 10～1: 1, adds continued reaction 30～90min; It is 7～8 that sulfonated products uses alkali to be neutralized to pH, obtains alkylphenol formaldehyde oligopolymer sulphonate after steaming desolventizes.
2. a kind of technology for preparing alkylphenol formaldehyde oligopolymer sulphonate as claimed in claim 1 is characterized in that described alkylphenol R
1-OH, R
1Be C
8～C
24Straight chain, branched-chain alkyl phenol, or the mixed phenol of different alkane chains.
3. a kind of technology for preparing alkylphenol formaldehyde oligopolymer sulphonate as claimed in claim 1 is characterized in that described catalyzer is alkyl aryl sulphonic acid or alkylsulphonic acid.
4. a kind of technology for preparing alkylphenol formaldehyde oligopolymer sulphonate as claimed in claim 3 is characterized in that described alkyl aryl sulphonic acid molecular formula is R
2-Ar-SO
3H, R
2Be C
1～C
16Straight chain, branched-chain alkyl aryl sulfonic acid, or different alkane chain blended alkyl aryl sulphonic acid, Ar is phenyl, naphthyl or phenylbenzene.
5. a kind of technology for preparing alkylphenol formaldehyde oligopolymer sulphonate as claimed in claim 3 is characterized in that described alkylsulphonic acid molecular formula is R
3-SO
3H, R
3Be C
8～C
24Straight chain, branched-chain alkyl sulfonic acid, or different alkane chain blended alkylsulphonic acid.
6. a kind of technology for preparing alkylphenol formaldehyde oligopolymer sulphonate as claimed in claim 1 is characterized in that described solvent is C
6～C
20Alkane or halohydrocarbon.
7. a kind of technology for preparing alkylphenol formaldehyde oligopolymer sulphonate as claimed in claim 6 is characterized in that described C
6～C
20Alkane is normal paraffin, isoparaffin, branched paraffin or naphthenic hydrocarbon.
8. a kind of technology for preparing alkylphenol formaldehyde oligopolymer sulphonate as claimed in claim 1 is characterized in that described halohydrocarbon is methylene dichloride, ethylene dichloride or trichloromethane.
9. a kind of technology for preparing alkylphenol formaldehyde oligopolymer sulphonate as claimed in claim 1 is characterized in that described sulphonating agent is oleum, sulfan or gas sulphur trioxide.
10. a kind of technology for preparing alkylphenol formaldehyde oligopolymer sulphonate as claimed in claim 9 is characterized in that described gas sulphur trioxide is the sulphur trioxide/air gas mixture that is obtained by combustion sulphur method, oleum acid gas formulation, sulfur dioxide liquid catforming or sulfan direct boiling method.
11. a kind of technology for preparing alkylphenol formaldehyde oligopolymer sulphonate as claimed in claim 10, the volume(tric)fraction that it is characterized in that sulphur trioxide in described sulphur trioxide/air gas mixture is in 5～20% scopes.
12. a kind of technology for preparing alkylphenol formaldehyde oligopolymer sulphonate as claimed in claim 1 is characterized in that the alkali in the described step (1) is mineral alkali or organic bases.
13. a kind of technology for preparing alkylphenol formaldehyde oligopolymer sulphonate as claimed in claim 12 is characterized in that described mineral alkali is sodium hydroxide, Pottasium Hydroxide or ammoniacal liquor.
14. a kind of technology for preparing alkylphenol formaldehyde oligopolymer sulphonate as claimed in claim 12 is characterized in that described organic bases is monoethanolamine, diethylolamine, trolamine or tetra-allkylammonium.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104774645A (en) * | 2014-01-09 | 2015-07-15 | 上海汉遥新材料科技有限公司 | Preparation method of low-temperature polyether-type viscous crude demulsifying agent |
| CN106031854A (en) * | 2015-03-20 | 2016-10-19 | 中国石油化工股份有限公司 | Anionic oligomeric surfactant and preparation method thereof |
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| CN104774645A (en) * | 2014-01-09 | 2015-07-15 | 上海汉遥新材料科技有限公司 | Preparation method of low-temperature polyether-type viscous crude demulsifying agent |
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| CN106031854A (en) * | 2015-03-20 | 2016-10-19 | 中国石油化工股份有限公司 | Anionic oligomeric surfactant and preparation method thereof |
| CN106031854B (en) * | 2015-03-20 | 2018-03-20 | 中国石油化工股份有限公司 | A kind of anionic oligo surfactant and preparation method thereof |
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