CN105170018A - Fluorosurfactant free of perfluorooctanoic acid as well as preparation method and process system of fluorosurfactant - Google Patents

Fluorosurfactant free of perfluorooctanoic acid as well as preparation method and process system of fluorosurfactant Download PDF

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CN105170018A
CN105170018A CN201510635307.3A CN201510635307A CN105170018A CN 105170018 A CN105170018 A CN 105170018A CN 201510635307 A CN201510635307 A CN 201510635307A CN 105170018 A CN105170018 A CN 105170018A
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fluorine
caprylic acid
perfluoro caprylic
surfactant
containing surfactant
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CN105170018B (en
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刘皓
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Chengdu Chenguang Boda New Material Co.,Ltd.
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CHENGDU CHENGUANG FLUORO & SILICONE ELASTOMERS Co Ltd
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Abstract

The invention discloses a fluorosurfactant free of perfluorooctanoic acid as well as a preparation method and a process system of the fluorosurfactant. The fluorosurfactant is a repeated structure unit which comprises at least one oxoperfluoropropenyl and one or a combination of more of perfluoromethoxyl, a Y group and oxoperfluorovinyl and is provided with a carboxyl group or carboxylate at one end. The fluorosurfactant is a fluoropolymer with the C-O-C ether bond structure as the main structural body; in view of indexes, the fluorosurfactant does not contain perfluorooctanoic acid with a 8-C straight-chain structure or salt of the perfluorooctanoic acid, is easily decomposed in nature and is proved to be harmless to human bodies, the peroxide value is 0.001%-0.1%, the surface tension is 10-30 mN/m, and the fluorosurfactant has an amphiphilic structure of a surfactant.

Description

A kind of not containing fluorine-containing surfactant and preparation method thereof and the process system of perfluoro caprylic acid
Technical field
The present invention is a kind of not containing fluorine-containing surfactant and preparation method thereof and the process system of perfluoro caprylic acid, is specifically related to be used as fluoropolymer that surfactant uses and synthetic method thereof and process system, belongs to organic synthesis field.
Background technology
Fluoropolymer is the special basic material that a class has high added value, and its development is in close relations with the user demand of the stratospheres such as military affairs, Aeronautics and Astronautics and nuclear industry.But based on domestic fluoropolymer manufacture Problems existing, we know, the qualitative factor of the fluoropolymer that current domestic enterprise produces is lower, can not meet the need of market, produce main or based on compared with the fluorine-containing product of the macromolecule of low side, as: four fluorine emulsions, tetrafluoro powder etc., particularly still need import as high value added products such as perfluoroelastomers, fluorine ether oils, therefore, industrial development is subject to yoke.
Fluoropolymer is obtained by fluorinated monomers polymerize, according to the difference of monomer used and polymerization, the molecular structure of the fluoropolymer that can synthesize is also different, such as: the recovery method of hexafluoropropene in patent document CN103467242A(photooxidation reaction raffinate, what relate to 2013-12-25) forms polymer by photooxidation by hexafluoropropene polymerization in ultraviolet light reactor, then after distillation still, obtain PFPE semi-finished product, mean molecule quantity is generally 10 3~ 10 4between, in addition, tetrafluoroethylene monomer also polymerizable prepares fluoropolymer, and tetrafluoroethene is formed straight chain polymer by photooxidation under the action of uv light, and mean molecule quantity is generally 10 3~ 10 5between.The molecular weight of the fluorochemical polyether prepared by the synthetic method reported in above-mentioned patent is all greater than 10 3, and there is no typical surfactant amphiphilic structure, the hydrophilic and oleophilic group namely comprised in the molecular structure, can not form in solution surface the surface tension aligning and reduce solution, surfactant should not be used as and use.
The more three class fluorine-containing surfactants of industrial application have metal carboxylate, Sulfonates and phosphoric acid salt three kinds, and in above-mentioned three class fluorine-containing surfactants, phosphoric acid salt fluorine surfactant is poor relative to foam performance, although Sulfonates fluorine surfactant has better oxidative resistance relatively, to strong acid, electrolyte sensitiveness is little, but show perfluoro caprylic acid and salt thereof, perfluorooctane sulfonate and salt adverse effect thereof, due to perfluoro caprylic acid and the salt thereof of 8 carbon-chain structures, perfluorooctane sulfonate and salt thereof not easily decompose by the Nature, be easy to enrichment in natural environment, and, the perfluoro caprylic acid of 8 carbon linear chain structure and salt thereof and perfluorooctane sulfonate and salt thereof are also proved harmful, therefore, before 2006, Environmental Protection Agency (EPA) has just promulgated the forbidding decree of the decree of forbidding perfluorooctane sulfonate (PFOS) and salt thereof and the chemicals of restriction perfluorooctanoic acid (PFOA) and some decomposable asymmetric choice net generation PFOA.
For adapting to the existing market demand, patent document CN103724559A(mono-kind synthesizes the method for PFPE by PFPE peroxide, 2014-04-16) propose the intermediate product PFPE peroxide prepared by photooxidation method and be placed in inertia containing fluorous solvent, under Ultraviolet radiation condition, pass into perfluoroolefine, after perfluoroolefine and peroxide reactions, form stable per-fluoro polyether compound.Synthetic method described in document, the raw material adopted is the peroxide of PFPE, we know, peroxide is very unstable, heat is decomposition explosion extremely easily, therefore be difficult to realize suitability for industrialized production with above-mentioned explained hereafter PFPE, there is very large potential safety hazard, and, the PFPE molecular weight produced by this method is greater than 1500, and there is no hydrophilic radical structure, do not possess the typical amphiphilic structure of surfactant, the capillary effect reducing solution can not be played, complex manufacturing, need the peroxide first synthesizing PFPE, further react with perfluoropropene or tetrafluoroethene as raw material again, obtain peroxide value lower than 2*10 -6the PFPE of mmol/g.
Except above-mentioned preparation method, the preparation method of a patent document CN103073410(fluorine ether carboxylic acid surfactant, 2013.05.01) also proposed with fluorinated olefin monomers, oxygen, molecular weight regulator is raw material, at-40 ~-80 DEG C, photooxidation reaction is caused through ultraviolet light, hydrolysis, washing purifying prepares fluorine ether carboxylic acid finished product, in the method, introducing due to oxygen atom makes to contain oxygen atom as the fluorine ether carboxylic acid finished product strand inside of surfactant, contribute to the biodegradation of fluorine ether carboxylic acid surfactant, remaining in organism can be eliminated.But in actual application, we know, the chemical feature of product can not be characterized by the arbitrary strand in its structural formula or group, arbitrary strand in structural formula, group or substituent change all likely cause varying of product property, particularly in large-scale industrial production, even if the tiny characteristic of product or flaw do not show in the preparation process of laboratory, also be very likely exaggerated in large-scale industrial production, therefore, in modern industrial production, the qualified sole criterion of inspection product is not only to the qualitative detection of product, also be the important indicator of inspection product preparation process, after only having industrial products to reach technical requirement, guarantee suitability for industrialized production not eliminate by market.
Summary of the invention
The object of the present invention is to provide a kind of not containing the fluorine-containing surfactant of perfluoro caprylic acid, the fluoropolymer that this fluorine-containing surfactant is is main structure body with C-O-C diether linkage structure, as can be seen from index, this fluorine-containing surfactant does not contain perfluoro caprylic acid and the salt thereof of 8 carbon linear chain structure, easily be decomposed in the Nature, and be proved harmless, cross oxygen value and meet 0.001 ~ 1%, surface tension meets 10 ~ 30mN/m, has the amphiphilic structure of surfactant.
Another object of the present invention is to provide a kind of not containing the preparation method of the fluorine-containing surfactant of perfluoro caprylic acid; using perfluoroolefine, oxygen and Third monomer as reaction raw materials; successively through photooxidation, hydrolysis, except peroxide process and neutralization four steps obtain fluorine-containing surfactant finished product; finished product index meets not containing perfluoro caprylic acid and salt thereof; and there is the amphiphilic structure of surfactant, Suitable commercial large-scale production.
Another object of the present invention is to provide a kind of not containing the preparation method of the fluorine-containing surfactant of perfluoro caprylic acid, using perfluoroolefine, oxygen and Third monomer as reaction raw materials, configure three steps obtain fluorine-containing surfactant finished product through photooxidation, hydrolysis, salify successively, finished product index meets not containing perfluoro caprylic acid and salt thereof, and there is the amphiphilic structure of surfactant, the industrial production of suitable serialization, has the advantages such as product yield is high, product quality fluctuation is little.
Another object of the present invention is to provide a kind of prepares not containing the process system of the fluorine-containing surfactant of perfluoro caprylic acid, the corresponding photooxidation of this process system, hydrolysis, except peroxide process and neutralization procedure, adopt photooxidation reaction device, hydrolytic reaction pot, heat treatment reactor and neutralization reaction still respectively, for the industrial production of fluorochemical polyether surfactant finished product, fluorine-containing surfactant finished product index meets not containing perfluoro caprylic acid and salt thereof, and has the amphiphilic structure of surfactant.
Another object of the present invention is to provide a kind of prepares not containing the continuous process system of the fluorine-containing surfactant of perfluoro caprylic acid, the corresponding photooxidation of this process system, hydrolysis, salify configure three steps, adopt photooxidation reaction loop, hydrolysis unit and salify dispensing unit respectively, for the industrial production of fluorochemical polyether surfactant finished product, there is the advantages such as product yield is high, product quality fluctuation is little, fluorine-containing surfactant finished product index meets not containing perfluoro caprylic acid and salt thereof, and has the amphiphilic structure of surfactant.
The present invention is achieved through the following technical solutions: a kind of not containing the fluorine-containing surfactant of perfluoro caprylic acid, described fluorine-containing surfactant is hexafluoropropylene-based and be selected from the constitutional repeating unit of an end band carboxyl that in perfluoromethoxy, Y group, oxygen perfluorovinyl sulfide, the combination of one or more forms or carboxylate by least one oxygen, and described Y group is selected from or , R=halogen or hydrogen, this fluorine-containing surfactant meets:
Acid number (in NaOH): <150mg/g;
Cross oxygen value: 0.001 ~ 1%, can also be, 0.001 ~ 0.1%;
Boiling point: 130 ~ 300 DEG C;
Surface tension: 10 ~ 30mN/m;
Critical micelle concentration (CMC): 0.05 ~ 5%;
Perfluoro caprylic acid and salt thereof: 0.
Can know from the indication range of fluoropolymer, the fluorine-containing surfactant that the present invention relates to is containing the perfluoro caprylic acid mentioned and salt thereof in Environmental Protection Agency (EPA) the chemicals forbidding decree of promulgating in 2006, fluorine-containing surfactant product index meets the amphiphilic nature of surfactant, there is the feature of Organic fluoride end oleophyllie hydrophobic, carboxylic acid ammonium's hydrophilic and oleophobic, show good surfactant properties.
Described fluorine-containing surfactant meets following structural formula:
Or ,
Calculate by the molecular weight of polymer, the content of halogen or hydrogen: 1 ~ 15%, n:1 ~ 10, m/n:0.01 ~ 0.03, preferably, n:1 ~ 2.
The molecular weight of described fluorine-containing surfactant is 200 ~ 600.
From said structure, the main structure body of the fluorine-containing surfactant that the present invention relates to is the diether linkage structure of C-O-C, not containing 8 carbon linear chain structure, be easily decomposed in the Nature, and be proved harmless, separately, the molecular weight of fluorine-containing surfactant is 200 ~ 400, n:1 ~ 3, well balances the oleophylic of this material and the performance of hydrophilic radical, make the material synthesized by technique disclosed in this invention have good surface property, the surface tension of solution can be effectively reduced.
Not containing a preparation method for the fluorine-containing surfactant of perfluoro caprylic acid, comprise the following steps:
A: perfluoroolefine, oxygen and Third monomer are at the temperature of-20 ~-25 DEG C, obtained containing acyl fluorides end group product after photooxidation;
B: will be hydrolyzed containing acyl fluorides end group product, obtains the fluorochemical oligomeric compound of an end band carboxylic acid acidic-group;
C: the fluorochemical oligomeric compound that step B is obtained is carried out, except peroxide process, obtain and be less than an end band carboxylic acid of 1g/100g and the fluorine-containing oil-based polymer of salt thereof containing peroxy-radical;
D: rear acquisition fluorine-containing surfactant finished product is neutralized to the fluorine-containing oil-based polymer that step C obtains,
This fluorine-containing surfactant finished product meets:
Acid number: <150mg/g;
Cross oxygen value: 0.001 ~ 1%, preferably, 0.001 ~ 0.1%;
Boiling point: 130 ~ 300 DEG C;
Surface tension: 10 ~ 30mN/m;
Critical micelle concentration (CMC): 0.05 ~ 5%;
Perfluoro caprylic acid and salt thereof: 0,
Described Third monomer is at least containing alkene or the alkynes of a non-fluorine atom, as chloroacetylene, vinylidene, vinyl chloride etc.
By the fluorine-containing surfactant finished product end group carboxylic acid content >99% that this explained hereafter is obtained, selective height.
In described steps A, count in mass ratio, perfluoroolefine: Third monomer=(1 ~ 10): 1, further, perfluoroolefine: oxygen: Third monomer=(100 ~ 1): (100 ~ 1): 1, in synthesis technique, the rational proportion of above-mentioned raw materials determines the scope of the molecular weight of synthesized fluorine-containing surfactant and it crosses oxygen value content, make the molecular weight of fluorine-containing surfactant meet 200 ~ 400, it is crossed oxygen value and meets 0.001 ~ 1%.
In described steps A, photooxidation comprises: the temperature of perfluoroolefine controlled at-20 ~-25 DEG C, the mist of oxygen and Third monomer composition is passed in perfluoroolefine, ultraviolet lamp irradiation and duration of ventilation is kept to be after 2 ~ 20h, close ultraviolet lamp, exhaust, unreacted perfluoroolefine is reclaimed after room temprature evaporation, obtained containing acyl fluorides end group product.
In above-mentioned technological process, (unreacted) perfluoroolefine excessive in photo-oxidation process, rectifying need not be passed through, washing, the recovery process that alkalescence and drying etc. are complicated, after only needing simple evaporative condenser to reclaim, be directly used in synthetic reaction next time, this be due to, the strict proportioning controlling material and the time of staying of gas in still, greatly reduce the generation of point accessory substance, therefore, excessive raw material (perfluoroolefine) is by simply evaporation and condensation, be directly used in lower secondary response, without the need to the recycling process of complexity, the energy consumption greatly reduced and consumption of raw materials, improve commercial synthesis efficiency.
The irradiation power of described ultraviolet lamp controls at 100 ~ 1000W, high-pressure sodium lamp can be selected, select wavelength > 300nm, the selection of above-mentioned technological parameter effectively can control the mistake oxygen content of product, if the mistake oxygen content of fluorine-containing surfactant finished product is higher than 5%, there is process safety hidden danger, in subsequent processes, easily set off an explosion, cause equipment investment cost high, product yield is low waits impact.
In the present invention, photooxidation reaction equation is as follows:
Wherein, Thirdmonomer represents Third monomer.
Hydrolytic process is that the acyl fluorides end group product that contains produced by photooxidation reaction is hydrolyzed, and then remove the process of aqueous phase, in described step B, hydrolytic process comprises:
B.1: by obtained to deionized water and steps A containing after the mixing of acyl fluorides end group product, stir;
B.2: the temperature that B.1 rate-determining steps prepares liquid phase fluid in material is 30 ~ 50 DEG C, continue to step B.1 prepare in material add steps A obtained containing acyl fluorides end group product, adding speed is 1 ~ 100L/H, and mixing time controls at 0.5 ~ 5h;
B.3: stir after stopping, static layering, after removing upper water, obtain the fluorochemical oligomeric compound of an end band carboxylic acid acidic-group.
Hydrolysis equation containing acyl fluorides end group product is as follows:
Generally speaking, in hydrolytic process, count in mass ratio, described deionized water: what steps A was obtained contains acyl fluorides end group product=(1 ~ 5): 1, further, deionized water: what steps A was obtained contains acyl fluorides end group product=(1.5 ~ 2): 1, the choose reasonable of this proportioning can ensure the method for the fluorine-containing oligomer after being hydrolyzed easily via static layering, and aqueous phase separation, can not emulsion be formed, avoid the phenomenon occurring being separated.
In described step D, N-process comprises:
D.1: after the end band carboxylic acid that step C is obtained and the fluorine-containing oil-based polymer of salt thereof and deionized water mixing, stir;
D.2: D.1 prepare in material to step and add alkali metal hydroxide aqueous solution or ammonia aqueous solution, obtain fluorine-containing surfactant finished product.
The reaction equation of N-process is as follows:
Not containing a preparation method for the fluorine-containing surfactant of perfluoro caprylic acid, described preparation method is continuous prodution process, comprises the following steps:
A: perfluoroolefine, oxygen and Third monomer continuous feed under the pressure of the temperature of 0 ~ 20 DEG C and 0.1 ~ 0.5Mpa, obtained containing acyl fluorides end group product after photooxidation;
B: after being hydrolyzed containing acyl fluorides end group product, being separated, obtain the fluorochemical oligomeric compound of an end band carboxylic acid acidic-group;
C: the fluorochemical oligomeric compound obtained in step B, after salify configuration, obtains fluorine-containing surfactant finished product,
This fluorine-containing surfactant finished product meets:
Acid number: <150mg/g;
Cross oxygen value: 0.001 ~ 0.1%, preferably, 0.001 ~ 0.1%;
Boiling point: 130 ~ 300 DEG C;
Surface tension: 10 ~ 30mN/m;
Critical micelle concentration: 0.05 ~ 5%;
Perfluoro caprylic acid and salt thereof: 0,
Described Third monomer is at least containing alkene or the alkynes of a non-fluorine atom, as chloroacetylene, vinylidene, vinyl chloride etc.
Above-mentioned preparation method provides a kind of industrial processes that can continue charging and discharging, change the potential safety hazard that when conventional batch is produced, product is in use reserved, the oxygen value excessively of the fluorine-containing surfactant finished product produced can control between 0.001 ~ 1%, preferably control in the scope of 0.001 ~ 0.1%, need not any process be carried out, just can apply downstream and produce.
In described steps A, the mixed material of perfluoroolefine, oxygen and Third monomer composition completes photooxidation reaction under UV-irradiation, keep the lasting charging of mixed material and the prolonged exposure of ultraviolet light, after the perfluoroolefine that gas-liquid separation is reclaimed in product, obtain containing acyl fluorides end group product.
The charging rate of described mixed material controls at 1 ~ 100L/H; Described ultraviolet lamp is UVLED lamp, and irradiation power controls at 1 ~ 100W, and selection wavelength is 300 ~ 410nm, the impact of selection on product index of above-mentioned data shows: wavelength is single, reaction efficiency is high, and no coupling product is produced, the large-scale production of suitability for industrialized.
In described steps A, count in mass ratio, perfluoroolefine: Third monomer=(1 ~ 10): 1, further, perfluoroolefine: oxygen: Third monomer=(100 ~ 1): (100 ~ 1): 1, the choose reasonable of above-mentioned technological parameter effectively can control the molecular weight ranges of fluorine-containing surfactant and it crosses the content of oxygen value, improves industrial usability.
Hydrolytic process is that the acyl fluorides end group product that contains produced by photooxidation reaction is hydrolyzed, then the process of aqueous phase is removed, in described step B, be hydrolyzed containing adding deionized water in acyl fluorides end group product, what maintenance was hydrolyzed continues to carry out, be separated after removing gas in hydrolysate and water, obtain the fluorochemical oligomeric compound of an end band carboxylic acid acidic-group.
Count in mass ratio, described deionized water: containing acyl fluorides end group product=(1 ~ 5): 1, further, deionized water: what steps A was obtained contains acyl fluorides end group product=(1.5 ~ 2): 1, the choose reasonable of this proportioning can ensure the method for the fluorine-containing oligomer after being hydrolyzed easily via static layering, and aqueous phase separation, can not emulsion be formed, avoid the phenomenon occurring being separated.
In described step C, salify configuration comprises the following steps:
C.1: the fluorochemical oligomeric compound of the end band carboxylic acid acidic-group that step B obtains is washed and after water-oil separating, obtains fluorochemical polyether carboxylic acid semi-finished product;
C.2: fluorochemical polyether carboxylic acid semi-finished product are refined, fluorochemical polyether carboxylic acid finished product is obtained;
C.3: in fluorochemical polyether carboxylic acid finished product and after, obtained fluorochemical polyether surfactant finished product.
The fluorochemical oligomeric compound of one end band carboxylic acid acidic-group is through washing the inorganic acid that can remove in fluorochemical oligomeric compound, fluorochemical polyether carboxylic acid finished product is obtained after the water added in water-oil separating removing water-washing process, described step C.2 in, refining comprising carries out preheating and de-low process to fluorochemical polyether carboxylic acid semi-finished product, preheat temperature controls at 180 ~ 220 DEG C, the object of preheating guarantees that reaction mass reaches the feeding temperature required by technique and remains unchanged before entering reaction system, guarantee industrial production efficiency, de-low energy deviates from the water and low molecule that dissolve in fluorochemical polyether carboxylic acid semi-finished product, the molecular weight of de-low rear fluorochemical polyether carboxylic acid finished product controls 100 ~ 300.
Described step C.3 in, neutralization is the process adding alkaline, inorganic salts and deionized water in fluorochemical polyether carboxylic acid finished product, count in mass ratio, fluorochemical polyether carboxylic acid finished product: alkaline, inorganic salts: deionized water=(20 ~ 30): (5 ~ 10): (10 ~ 30).
Described alkaline, inorganic salts is the mixture of one or more compositions in ammonium salt, sodium salt, sylvite.
A kind of process system preparing the fluorine-containing surfactant not containing perfluoro caprylic acid, described process system comprises the photooxidation reaction device, hydrolytic reaction pot, heat treatment reactor and the neutralization reaction still that are communicated with successively, photooxidation reaction device is connected to perfluoroolefine storage tank and breather pipe, breather pipe is the water sealing (sealing water) pipe passing into mist in photooxidation reaction device, described mist is made up of oxygen and Third monomer, described neutralization reaction still is connected with the finished product storage tank storing fluorochemical polyether surfactant, and described fluorochemical polyether surfactant meets:
Acid number (in NaOH): <150mg/g;
Cross oxygen value: 0.001 ~ 0.1%, preferably, 0.001 ~ 0.1%;
Boiling point: 130 ~ 300 DEG C;
Surface tension: 10 ~ 30mN/m;
Critical micelle concentration (CMC): 0.05 ~ 5%;
Perfluoro caprylic acid and salt thereof: 0,
Described Third monomer is at least containing alkene or the alkynes of a non-fluorine atom, as chloroacetylene, vinylidene, vinyl chloride etc.
The present invention relates to reaction raw materials perfluoroolefine, oxygen and Third monomer are successively through photooxidation reaction device, hydrolytic reaction pot, heat treatment reactor, the industrial production system of fluorochemical polyether surfactant prepared by neutralization reaction still, the fluorochemical polyether surfactant finished product prepared is not containing perfluoro caprylic acid and salt thereof, surface tension 10 ~ 30mN/m, there is the amphiphilic nature of surfactant, cross oxygen value can control between 0.001 ~ 1%, preferably control in the scope of 0.001 ~ 0.1%, eliminate the production safety hidden danger of downstream manufacturers, possesses good commercial application prospect.
Described photooxidation reaction device is provided with the stainless steel equipment of quartzy sheath and thermocouple in being, described quartzy sheath to be evenly distributed on centered by photooxidation reaction device axis circumferentially, and be provided with two-layer from inside to outside along photooxidation reaction device axis, described photooxidation reaction device is provided with exhaust outlet.
Described photooxidation reaction device is provided with reflux condensing tube, perfluoroolefine from perfluoroolefine storage tank is sent in photooxidation reaction device through reflux condensing tube, the condensation temperature of reflux condensing tube is-30 ~-60 DEG C, the effect of reflux condensing tube ensures to be lowered the temperature by condenser by the perfluoroolefine of the gaseous mixture entrained with such as oxygen, is back in photooxidation reaction device after condensation again.
The effect of quartz sheath is built-in for ultraviolet lamp; First perfluoroolefine joins in photooxidation reaction device by condenser, and then, the mist of oxygen and Third monomer composition blasts in photooxidation reaction device by water sealing (sealing water) pipe; Reflux condensing tube can control the temperature in reactor, it is made to remain between-30 ~-20 DEG C, and the temperature of inside reactor is measured in real time by thermoelectricity lotus root, exhaust outlet, for discharging unreacted perfluoroolefine, continues to serve as photooxidation raw material and uses after recyclable, condensation.
Described hydrolytic reaction pot is the consersion unit of carbon steel lining fluorine or carbon steel spraying polytetrafluoro coating, it is advantageous that and prevent reaction system quilt, discharge highly acid material corroded in hydrolytic process, the service life of extension device, reduce production cost and equipment investment, hydrolytic reaction pot is provided with the liquid phase charge door added for photooxidation reaction product and deionized water, evacuation port and cooling jacket, agitator is provided with in hydrolytic reaction pot, evacuation port is set and can discharges the sour gas produced in hydrolytic process in time, under normal circumstances, also thermocouple is provided with in hydrolytic reaction pot, for the real time temperature of measurement device inside.
In actual production process, first in hydrolytic reaction pot, deionized water is added, and then add photooxidation reaction product (containing acyl fluorides end group product), turn on agitator, and cooling water is passed in cooling jacket, then continue to add photooxidation reaction product in hydrolytic reaction pot by liquid phase charge door, by by-pass valve control aperture, adjustment adds speed, adding speed is 1 ~ 100L/H, can be controlled in 20 ~ 30L/H further, the amount simultaneously entering cooling jacket by controlled cooling model water carrys out the temperature of liquid phase fluid in controlled hydrolysis reactor between 10 ~ 50 DEG C, further temperature-controllable is between 30 ~ 40 DEG C.
All be added to after in hydrolytic reaction pot until photooxidation reaction product, continue stirring 0.5 ~ 2h, further control mixing time is at 0.8 ~ 1h, stop subsequently stirring, stratification, remove upper water, obtain hydrolysate (the fluorochemical oligomeric compound of an end band carboxylic acid acidic-group) and deliver to heat treatment reactor, described heat treatment reactor is the consersion unit of carbon steel lining fluorine or carbon steel polytetrafluoroethylene spray, and described heat treatment reactor is provided with agitator, heating inner coil pipe, heating jacket, conduction oil device.
After hydrolysate enters heat treatment reactor, open conduction oil device and heat conduction oil circulating pump, turn on agitator, conduction oil passes through heating jacket, material in heat treatment reactor is heated, control temperature of charge 300 DEG C in still, control further between 200 ~ 260 DEG C, reacting system pressure remains on 4Mpa, keep this temperature and pressure, and maintain 1 ~ 6h, control further in 2 ~ 3 hours, make active oxygen (peroxide) decomposes of hydrolysate, the active o content obtaining heat-treated products (the fluorine-containing oil-based polymer of an end band carboxylic acid and salt thereof) is less than 1g/100g, further, active o content is less than 1 ~ 0.8g/100g.
Described neutralization reaction still is stainless steel cauldron, neutralization reaction still is provided with the charge door and cooling water jecket that add for alkaline solution and deionized water, in neutralization reaction still, is provided with agitator.
After heat-treated products and deionized water enter neutralization reaction still, turn on agitator, after abundant mixing, slowly add alkaline solution (as: the alkali metal aqueous solution or ammonia aqueous solution), in and the acidity of heat-treated products, control the addition of the alkali metal aqueous solution or ammoniacal liquor, keep the pH value of the fluoropolymer aqueous solution between 8 ~ 11, control further between 9 ~ 10, in N-process, cooling water passes into in cooling water jecket, by controlled cooling model discharge, the control of realization response system temperature, control between 15 ~ 50 DEG C, further, temperature controls at 20 ~ 40 DEG C as good.
In above process, the one in alkali metal aqueous solution selected from sodium hydroxide, potassium hydroxide.
A kind of continuous process system preparing the fluorine-containing surfactant not containing perfluoro caprylic acid, described process system comprises the photooxidation reaction loop be connected successively, hydrolysis unit and salify dispensing unit, photooxidation reaction loop comprises perfluoroolefine storage tank, Third monomer storage tank, photooxidation reaction device and gas-liquid separator, air and liquid mixer is connected with at the entrance of photooxidation reaction device, perfluoroolefine, Third monomer and oxygen send into photooxidation reaction device through air and liquid mixer, gas-liquid separator is connected in the outlet of photooxidation reaction device, the gaseous phase outlet of gas-liquid separator is connected with perfluoroolefine storage tank, the liquid-phase outlet of gas-liquid separator is connected with hydrolysis unit, salify dispensing unit is connected with the finished product storage tank storing fluorochemical polyether surfactant, and described fluorochemical polyether surfactant meets:
Acid number (in NaOH): <150mg/g;
Cross oxygen value: 0.001 ~ 0.1%, preferably, 0.001 ~ 0.1%;
Boiling point: 130 ~ 300 DEG C;
Surface tension: 10 ~ 30mN/m;
Critical micelle concentration (CMC): 0.05 ~ 5%,
Perfluoro caprylic acid and salt thereof: 0,
Described Third monomer is at least containing alkene or the alkynes of a non-fluorine atom, as chloroacetylene, vinylidene, vinyl chloride etc.
The continuous process system that the present invention relates to is primarily of photooxidation reaction loop, hydrolysis unit and salify dispensing unit three part composition, raw material perfluoroolefine, Third monomer light and oxygen are obtained containing acyl fluorides end group product behind oxidation reaction loop, unreacted perfluoroolefine is recycled by reuse, containing the fluorochemical oligomeric compound of acyl fluorides end group product obtained end band carboxylic acid acidic-group after hydrolysis, and then through the obtained fluorine-containing surfactant finished product of salify configuration, this process system can adopt the mode of lasting charging and discharging, change in the past traditional batch method produce time product molecular weight distribution wide, a large amount of high boiling accessory substance is had to generate, output per single reactor is low, total yield of products is lower than 15%, oxygenated products contained oxygen value and was greater than 2%, reprocessing loss is large, the defects such as product quality fluctuation is large, continuous print suitability for industrialized production can be realized.
Described photooxidation reaction loop also comprises the condenser of precooling reaction raw materials and precooling gas-liquid separator gas recovery, and the quantity of described condenser is three groups, and one group is connected on Third monomer storage tank; One group is connected on perfluoroolefine storage tank; One group is connected between perfluoroolefine storage tank and the gaseous phase outlet of gas-liquid separator, and the object of use condenser to raw material precooling is: guarantee that reaction mass reaches the feeding temperature required by technique and remains unchanged before entering reaction system, guarantee industrial production efficiency.
For convenience of the lasting charging of reaction raw materials, described photooxidation reaction device is the tubular reactor be composed in series by glass tube, series connection direction along glass tube is evenly arranged the ultraviolet aperture of more than a group, often organize ultraviolet aperture to be made up of the LED uviol lamp pearl be circumferentially evenly arranged apart from glass tube external diameter 1 ~ 5mm, the light-emitting area of LED uviol lamp pearl is corresponding on glass tube.
For ensureing the smooth production of process system, the quantity of described glass tube is 50 ~ 100, and the length of every root glass tube is 1 ~ 2m.
Further, the quantity of described LED uviol lamp pearl is 50 ~ 100, and the wavelength of each LED uviol lamp pearl is 365 ~ 405nm.
Described hydrolysis unit comprises circulation, the hydrolysis reactor be connected with the liquid-phase outlet of gas-liquid separator, is connected the three phase separator that hydrolysis reactor exports, the entrance of hydrolysis reactor is all connected with circulation with the aqueous phase outlet of three phase separator, be provided with tail gas evacuation port at the gaseous phase outlet of three phase separator, the oil phase outlet of three phase separator is provided with the fluorochemical oligomeric compound storage tank be connected with salify dispensing unit.
Mixing baffle is provided with in described hydrolysis reactor.
Described hydrolysis reactor is the tubular reactor be composed in series by steel lining resin pipeline, and the internal diameter of steel lining resin pipeline is 20 ~ 40mm.
In said structure, the water that circulation provides hydrolytic process to use; Mixing baffle in hydrolysis reactor, ensure that the abundant reaction of water and photooxidation reaction product (containing acyl fluorides end group product), hydrolysis reactor adopts tubular reactor, the mode of production continuing charging and discharging can be realized, three phase separator delivered to by material after hydrolysis, tail gas evacuation port can discharge the sour gas produced in hydrolytic process in time, and the fluorochemical oligomeric compound of an end band carboxylic acid acidic-group is delivered to fluorochemical oligomeric compound storage tank by oil phase outlet.
The salify dispensing unit that the present invention relates to is made up of three parts, be respectively remove inorganic acid in fluorochemical oligomeric compound washing process, deviate from the water and low molecule that dissolve in fluorochemical polyether carboxylic acid semi-finished product and obtain the rectification flow of fluorochemical polyether carboxylic acid finished product, by in fluorochemical polyether carboxylic acid finished product and rear obtained fluorochemical polyether surfactant in and flow process, its process system is as follows:
Described salify dispensing unit comprise successively be connected washing process, rectification flow and in and flow process, washing process comprises the washing kettle, the first oil water separator and the second oil water separator that are connected with fluorochemical oligomeric compound storage tank successively, washing kettle entrance, the first oil water separator aqueous phase outlet, the second oil water separator aqueous phase outlet are all connected with circulation, and the second oil water separator oil phase outlet is provided with the fluorochemical polyether carboxylic acid semi-finished product storage tank be connected with rectification flow; During finished product storage tank is connected to and in flow process.
Described rectification flow comprises the preheater that is connected with fluorochemical polyether carboxylic acid semi-finished product storage tank successively and de-low device, described de-low device is provided with in the fluorochemical polyether carboxylic acid finished product storage tank that is connected with flow process and evacuation port.
In described and flow process comprise in and batch tank, in and batch tank entrance be connected with alkali lye batch tank and pure water batch tank, in and batch tank export be connected finished product batch tank.
Described preheater and de-low device are all connected with the heat-conducting oil system providing thermal source.
For the controllability of reaction temperature when guarantee photooxidation reaction and hydrolysis, described photooxidation reaction device, condenser, Third monomer storage tank, perfluoroolefine storage tank, hydrolysis reactor are all connected with the freezing liquid circulatory system of control temperature.
The condenser connecting gas-liquid separator gaseous phase outlet and perfluoroolefine storage tank is provided with offgas outlet, described offgas outlet, tail gas evacuation port and evacuation port is connected with the tail gas purification tower of process tail gas, reduce environmental protection pressure.
The present invention compared with prior art, has the following advantages and beneficial effect:
(1) the present invention mainly solves the problem of existing fluorine-containing surfactant environmental pollution and the perfluoro caprylic acid of 8 carbon linear chain structure and the adverse effect of salt and perfluorooctane sulfonate and salt pair human body thereof thereof, propose the fluorine-containing surfactant that main structure body is C-O-C diether linkage structure, this structure is easy to be decomposed in the Nature, be proved harmless, and there is the amphiphilic structure of surfactant.
(2) fluorine-containing surfactant that the present invention relates to is the fluorine-containing oligomer not containing perfluoro caprylic acid and salt thereof, molecular weight can control between 200 ~ 600, crossing oxygen value can control in the scope of 0.001 ~ 1%, not only there is good surface active properties, when being applied in downstream manufacturers, peroxide bridge fracture not easily occurs and sets off an explosion, it also avoid downstream manufacturers is the production safety hidden danger that elimination peroxide bridge causes, and has commercial application value.
(3) in the structural formula met in the present invention, determine that the n value of fluorochemical polyether carboxylate is between 1 ~ 10, preferably 1 ~ 2, the well balance oleophylic of fluorine-containing surfactant and the performance of hydrophilic radical, except making it have good surface-active, the surface tension of solution can also be effectively reduced.
(4) preparation method involved in the present invention adopts perfluoroolefine, oxygen and Third monomer to be raw material, at the temperature of-20 ~-25 DEG C after photooxidation reaction, anamorphic zone acyl fluorides end group and molecular weight 100 ~ 1000 PFPE acyl fluorides (containing acyl fluorides end group product), and by hydrolysis, except peroxide process and neutralization procedure, obtain that there is amphiphilic structure, can align in solution surface, effective reduction solution surface tension and cross the fluorine-containing surfactant finished product of oxygen value full 0.001 ~ 1%, need not any process be carried out, just can apply downstream and produce.This preparation method's difference with the prior art is, reaction temperature is high, does not need refrigerant temperature to control at-45 DEG C, and therefore, without the need to cascade refrigeration unit, energy consumption reduces greatly, suitability for industrialized large-scale production.
(5) the present invention can adopt the production technology of serialization, with perfluoroolefine, oxygen and Third monomer are raw material, under the pressure of the temperature of 0 ~ 20 DEG C and 0.1 ~ 0.5Mpa after photooxidation reaction, again by hydrolysis, salify configuration obtained the fluorine-containing surfactant finished product that oxygen value meets 0.001 ~ 1%, photooxidation reaction and hydrolysis adopt and continue charging and discharge method, particularly in photooxidation reaction under the control of temperature and pressure and the cooperation of lasting charging and discharging method, the strict proportioning controlling oxygen and perfluoroolefine and reaction time in the reactor, essentially eliminate the back mixing effect of oxidation product in reactor, to the oxygen value of crossing of fluorine-containing surfactant, there is good control effects.
(6) by cooperation and the suitably adjustment of parameter in each step of preparation technology of the present invention, the n value of fluorochemical polyether carboxylate can be precisely controlled, and molecular weight must control between 200 ~ 600, obtain the oligomer of fluorochemical polyether, increase its surface-active, the end group carboxylic acid content of the fluorine-containing surfactant produced can control at >99%, selective height.
(7) the present invention is reasonable in design, perfluoroolefine excessive in photo-oxidation process, rectifying need not be passed through, washing, the recovery process that alkalescence and drying etc. are complicated, after being reclaimed, can be directly used in synthetic reaction next time by simple evaporative condenser, without the need to the recycling process of complexity, the energy consumption greatly reduced and consumption of raw materials.
(8) the present invention can realize the industrial production of serialization, photooxidation reaction and hydrolytic process can adopt the pipeline reactor that can continue charging and discharging, change product molecular weight distribution when traditional batch method is produced wide, a large amount of high boiling accessory substance is had to generate, output per single reactor is low, and total yield of products is lower than 15%, and oxygenated products contained oxygen value and is greater than 2%, the defects such as reprocessing loss is large, and product quality fluctuation is large.
(9) preparation method of the present invention corresponding batch production process system and continuous production technology system and design respectively, for obtaining the fluorine-containing surfactant finished product that oxygen value meets 0.001 ~ 1%, in batch production process system, adopt the rational proportion of perfluoroolefine, oxygen and Third monomer, and the control of reaction temperature and pressure, realize the control of crossing oxygen value content in product; In continuous production technology system, on the basis of above-mentioned control mode, adopt the mode of continuous feed and discharging, further control oxygen and the perfluoroolefine time of staying in the reactor, realize the control of crossing oxygen value content in product, prove through practical operation, said method all can obtain the fluorine-containing surfactant finished product not containing perfluoro caprylic acid and salt thereof that oxygen value meets 0.001 ~ 0.1%, has good market value.
(10) the pipeline continuous reaction of the present invention's employing, the material back mixing problem that tank reactor brings can be eliminated, to product, proportioning between raw material achieves strict control, the time of staying of raw material in pipeline reactor is identical, so the molecular weight uniform of the product obtained is consistent, the excursion of n value controls further between 1 ~ 2, the n value scope of tank reactor intermittently operated is very large between 1 ~ 20, therefore adopt continuous process system to produce and do not improve 6 times containing effective productivity ratio batch tank reactor of the PFPE fluorine-containing surfactant of perfluoro caprylic acid, the yield of perfluor fluorine-containing surfactant can up to more than 95%, and the finished product yield of batch tank reactor only has 15%, consumption of raw materials is very large, and accessory substance is many cannot process, bring very large environmental problem.
(11) continuous process that the present invention adopts produces the yield in unit time that can improve fluorine-containing surfactant finished product, reaction belongs to gas-liquid two-phase reaction, batch (-type) tank reactor is due to the structure problem of equipment own, well can not control the time of staying of vapor-phase reactant in reactor, so the yield in unit time of batch (-type) tank reactor is very low, only has 0.5 ~ 1kg/h, continuous flow process is adopted to produce not containing the fluorine-containing surfactant of perfluoro caprylic acid, owing to adding the time of staying of gaseous phase materials in reaction system, Forced Mixing gas phase and liquid phase material, the yield in unit time of the product produced with continuous flow process is improved, 60kg/ hour can be reached, it is 60 times of tank reactor.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1:
The present embodiment proposes a kind of not containing the fluorine-containing surfactant of perfluoro caprylic acid, this fluorine-containing surfactant is hexafluoropropylene-based and be selected from the constitutional repeating unit of an end band carboxyl that in perfluoromethoxy, Y group, oxygen perfluorovinyl sulfide, the combination of one or more forms or carboxylate by least one oxygen, and Y group is selected from , R=halogen, this fluorine-containing surfactant meets:
Acid number: 148mg/g;
Cross oxygen value: 0.001%;
Boiling point: 130 DEG C;
Surface tension: 10mN/m;
Critical micelle concentration: 0.05%;
Perfluoro caprylic acid and salt thereof: 0.
Embodiment 2:
The fluorine-containing surfactant that the present embodiment relates to is hexafluoropropylene-based and be selected from the constitutional repeating unit of an end band carboxyl that in perfluoromethoxy, Y group, oxygen perfluorovinyl sulfide, the combination of one or more forms or carboxylate by least one oxygen, and Y group is selected from , R=hydrogen, this fluorine-containing surfactant meets:
Acid number: 120mg/g;
Cross oxygen value: 1%;
Boiling point: 300 DEG C;
Surface tension: 30mN/m;
Critical micelle concentration: 5%;
Perfluoro caprylic acid and salt thereof: 0.
Embodiment 3:
The structure of the fluorine-containing surfactant that the present embodiment relates to be for:
Wherein, Y group is selected from , R=halogen,
Calculate by the molecular weight of polymer, the content of halogen or hydrogen: 1%, n:1, m/n:0.01.
Embodiment 4:
The structure of the fluorine-containing surfactant that the present embodiment relates to be for:
，
Wherein, Y group is selected from , R=hydrogen,
Calculate by the molecular weight of polymer, the content of halogen or hydrogen: 15%, n:10, m/n:0.03.
Embodiment 5:
The difference of the present embodiment and embodiment 1 is: the molecular weight of the fluorine-containing surfactant that the present embodiment relates to is 200.
Embodiment 6:
The difference of the present embodiment and embodiment 2 is: the molecular weight of the fluorine-containing surfactant that the present embodiment relates to is 600.
Embodiment 7:
The structure of the fluorine-containing surfactant that the present embodiment relates to be for:
Wherein, Y group is selected from , R=hydrogen,
Calculate by the molecular weight of polymer, the content of halogen or hydrogen: 8%, n:1, m/n:0.015.
The molecular weight of above-mentioned fluorine-containing surfactant is 255.
Embodiment 8:
The structure of the fluorine-containing surfactant that the present embodiment relates to be for:
，
Wherein, Y group is selected from , R=halogen,
Calculate by the molecular weight of polymer, the content of halogen or hydrogen: 11%, n:2, m/n:0.02.
The molecular weight of above-mentioned fluorine-containing surfactant is 360.
Embodiment 9:
The structure of the fluorine-containing surfactant that the present embodiment relates to be for:
，
Wherein, Y group is selected from , R=hydrogen,
Calculate by the molecular weight of polymer, the content of halogen or hydrogen: 7%, n:2, m/n:0.01.
The molecular weight of above-mentioned fluorine-containing surfactant is 300.
Embodiment 10:
The structure of the fluorine-containing surfactant that the present embodiment relates to be for:
Wherein, Y group is selected from , R=halogen,
Calculate by the molecular weight of polymer, the content of halogen or hydrogen: 14%, n:1, m/n:0.025.
The molecular weight of above-mentioned fluorine-containing surfactant is 280.
(detection method is undertaken by national standard) and statistics are detected to the index parameter of the fluorine-containing surfactant that embodiment 1 ~ 10 relates to, as shown in table 1.
Table 1
The concrete preparation method of embodiment 1 ~ 10 is illustrated below with several exemplary embodiments.
Embodiment 11:
The present embodiment is the preparation method not containing the fluorine-containing surfactant of perfluoro caprylic acid for embodiment 1, comprises the following steps:
A: perfluoroolefine, oxygen and Third monomer are at the temperature of-20 DEG C, obtained containing acyl fluorides end group product after photooxidation;
B: will be hydrolyzed containing acyl fluorides end group product, obtains the fluorochemical oligomeric compound of an end band carboxylic acid acidic-group;
C: the fluorochemical oligomeric compound that step B is obtained is carried out, except peroxide process, obtain and be less than an end band carboxylic acid of 1g/100g and the fluorine-containing oil-based polymer of salt thereof containing peroxy-radical;
D: rear acquisition fluorine-containing surfactant finished product is neutralized to the fluorine-containing oil-based polymer that step C obtains,
In above-mentioned steps, Third monomer is chloroacetylene.
Embodiment 12:
The present embodiment is the preparation method not containing the fluorine-containing surfactant of perfluoro caprylic acid for embodiment 2, comprises the following steps:
A: perfluoroolefine, oxygen and Third monomer are at the temperature of-25 DEG C, obtained containing acyl fluorides end group product after photooxidation;
B: will be hydrolyzed containing acyl fluorides end group product, obtains the fluorochemical oligomeric compound of an end band carboxylic acid acidic-group;
C: the fluorochemical oligomeric compound that step B is obtained is carried out, except peroxide process, obtain and be less than an end band carboxylic acid of 1g/100g and the fluorine-containing oil-based polymer of salt thereof containing peroxy-radical;
D: rear acquisition fluorine-containing surfactant finished product is neutralized to the fluorine-containing oil-based polymer that step C obtains,
In above-mentioned steps, Third monomer is vinyl chloride.
Embodiment 13:
The present embodiment is the preparation method not containing the fluorine-containing surfactant of perfluoro caprylic acid for embodiment 3, the difference of this preparation method and embodiment 11 is: in the steps A that the present embodiment relates to, the mass ratio of perfluoroolefine and Third monomer is 1:1, wherein, Third monomer is chloroacetylene, vinylidene, vinyl chloride etc.
Embodiment 14:
The present embodiment is the preparation method not containing the fluorine-containing surfactant of perfluoro caprylic acid for embodiment 4, the difference of this preparation method and embodiment 12 is: in the steps A that the present embodiment relates to, photooxidation comprises: control at-22 DEG C by the temperature of perfluoroolefine, the mist of oxygen and Third monomer composition is passed in perfluoroolefine, ultraviolet lamp irradiation and duration of ventilation is kept to be after 2h, close ultraviolet lamp, exhaust, unreacted perfluoroolefine is reclaimed after room temprature evaporation, obtained containing acyl fluorides end group product.
In the present embodiment, the irradiation power of ultraviolet lamp controls at 100W, and selection wavelength is 310nm.
Embodiment 15:
The present embodiment is the preparation method not containing the fluorine-containing surfactant of perfluoro caprylic acid for embodiment 5, and the difference of this preparation method and embodiment 11 is: in the step B that the present embodiment relates to, hydrolytic process comprises:
B.1: by obtained to deionized water and steps A containing after the mixing of acyl fluorides end group product, stir;
B.2: the temperature that B.1 rate-determining steps prepares liquid phase fluid in material is 30 DEG C, continue to step B.1 prepare in material add steps A obtained containing acyl fluorides end group product, adding speed is 1L/H, and mixing time controls at 0.5h;
B.3: stir after stopping, static layering, after removing upper water, obtain the fluorochemical oligomeric compound of an end band carboxylic acid acidic-group.
In the present embodiment, the mass ratio containing acyl fluorides end group product that deionized water and steps A obtain is 1:1.
Embodiment 16:
The present embodiment is the preparation method not containing the fluorine-containing surfactant of perfluoro caprylic acid for embodiment 6, and the difference of this preparation method and embodiment 12 is: in the step B that the present embodiment relates to, hydrolytic process comprises:
B.1: by obtained to deionized water and steps A containing after the mixing of acyl fluorides end group product, stir;
B.2: the temperature that B.1 rate-determining steps prepares liquid phase fluid in material is 50 DEG C, continue to step B.1 prepare in material add steps A obtained containing acyl fluorides end group product, adding speed is 100L/H, and mixing time controls at 5h;
B.3: stir after stopping, static layering, after removing upper water, obtain the fluorochemical oligomeric compound of an end band carboxylic acid acidic-group.
In the present embodiment, the mass ratio containing acyl fluorides end group product that deionized water and steps A obtain is 5:1.
Embodiment 17:
The present embodiment is the preparation method not containing the fluorine-containing surfactant of perfluoro caprylic acid for embodiment 7, and the difference of this preparation method and embodiment 11 is: in the step D that the present embodiment relates to, N-process comprises:
D.1: after the end band carboxylic acid that step C is obtained and the fluorine-containing oil-based polymer of salt thereof and deionized water mixing, stir;
D.2: D.1 prepare in material to step and add alkali metal hydroxide aqueous solution or ammonia aqueous solution, obtain fluorine-containing surfactant finished product.
Embodiment 18:
The present embodiment is the preparation method not containing the fluorine-containing surfactant of perfluoro caprylic acid for embodiment 8, comprises the following steps:
(A) temperature of perfluoroolefine is controlled at-24 DEG C, the mist that oxygen and Third monomer (as vinylidene) form is passed in perfluoroolefine, ultraviolet lamp irradiation and duration of ventilation is kept to be after 20h, close ultraviolet lamp, exhaust, unreacted perfluoroolefine is reclaimed after room temprature evaporation, obtained containing acyl fluorides end group product, wherein, the mass ratio of perfluoroolefine, oxygen and Third monomer meets 100:100:1, the irradiation power of ultraviolet lamp controls at 1000W, can select high-pressure sodium lamp, selection wavelength is 450nm.
(B) will be hydrolyzed containing acyl fluorides end group product, hydrolytic process comprises:
B.1: by obtained to deionized water and steps A containing after the mixing of acyl fluorides end group product, stir;
B.2: the temperature that B.1 rate-determining steps prepares liquid phase fluid in material is 35 DEG C, continue to step B.1 prepare in material add steps A obtained containing acyl fluorides end group product, adding speed is 40L/H, and mixing time controls at 3h;
B.3: stir after stopping, static layering, after removing upper water, obtain the fluorochemical oligomeric compound of an end band carboxylic acid acidic-group,
In said hydrolyzed process, the mass ratio containing acyl fluorides end group product that deionized water and steps A obtain controls at 1.5:1.
(C) the fluorochemical oligomeric compound that step B is obtained is carried out, except peroxide process, obtain and be less than an end band carboxylic acid of 1g/100g and the fluorine-containing oil-based polymer of salt thereof containing peroxy-radical;
(D) neutralize the fluorine-containing oil-based polymer that step C obtains, N-process comprises:
D.1: after the end band carboxylic acid that step C is obtained and the fluorine-containing oil-based polymer of salt thereof and deionized water mixing, stir;
D.2: D.1 prepare in material to step and add ammonia aqueous solution, obtain fluorine-containing surfactant finished product.
Embodiment 19:
The present embodiment is the preparation method not containing the fluorine-containing surfactant of perfluoro caprylic acid for embodiment 9, comprises the following steps:
(A) temperature of perfluoroolefine is controlled at-25 DEG C, the mist that oxygen and Third monomer (as chloroacetylene) form is passed in perfluoroolefine, ultraviolet lamp irradiation and duration of ventilation is kept to be after 18h, close ultraviolet lamp, exhaust, unreacted perfluoroolefine is reclaimed after room temprature evaporation, obtained containing acyl fluorides end group product, wherein, the mass ratio of perfluoroolefine, oxygen and Third monomer meets 1:1:1, the irradiation power of ultraviolet lamp controls at 350W, can select high-pressure sodium lamp, selection wavelength is 330nm.
(B) will be hydrolyzed containing acyl fluorides end group product, hydrolytic process comprises:
B.1: by obtained to deionized water and steps A containing after the mixing of acyl fluorides end group product, stir;
B.2: the temperature that B.1 rate-determining steps prepares liquid phase fluid in material is 40 DEG C, continue to step B.1 prepare in material add steps A obtained containing acyl fluorides end group product, adding speed is 60L/H, and mixing time controls at 2h;
B.3: stir after stopping, static layering, after removing upper water, obtain the fluorochemical oligomeric compound of an end band carboxylic acid acidic-group,
In said hydrolyzed process, the mass ratio containing acyl fluorides end group product that deionized water and steps A obtain controls at 2:1.
(C) the fluorochemical oligomeric compound that step B is obtained is carried out, except peroxide process, obtain and be less than an end band carboxylic acid of 1g/100g and the fluorine-containing oil-based polymer of salt thereof containing peroxy-radical;
(D) neutralize the fluorine-containing oil-based polymer that step C obtains, N-process comprises:
D.1: after the end band carboxylic acid that step C is obtained and the fluorine-containing oil-based polymer of salt thereof and deionized water mixing, stir;
D.2: D.1 prepare in material to step and add alkali metal hydroxide aqueous solution, obtain fluorine-containing surfactant finished product.
Embodiment 20:
The present embodiment is the preparation method not containing the fluorine-containing surfactant of perfluoro caprylic acid for embodiment 10, comprises the following steps:
(A) temperature of perfluoroolefine is controlled at-23 DEG C, the mist that oxygen and Third monomer (as vinyl chloride) form is passed in perfluoroolefine, ultraviolet lamp irradiation and duration of ventilation is kept to be after 15h, close ultraviolet lamp, exhaust, unreacted perfluoroolefine is reclaimed after room temprature evaporation, obtained containing acyl fluorides end group product, wherein, the mass ratio of perfluoroolefine, oxygen and Third monomer meets 50:50:1, the irradiation power of ultraviolet lamp controls at 800W, can select high-pressure sodium lamp, selection wavelength is 360nm.
(B) will be hydrolyzed containing acyl fluorides end group product, hydrolytic process comprises:
B.1: by obtained to deionized water and steps A containing after the mixing of acyl fluorides end group product, stir;
B.2: the temperature that B.1 rate-determining steps prepares liquid phase fluid in material is 45 DEG C, continue to step B.1 prepare in material add steps A obtained containing acyl fluorides end group product, adding speed is 55L/H, and mixing time controls at 4h;
B.3: stir after stopping, static layering, after removing upper water, obtain the fluorochemical oligomeric compound of an end band carboxylic acid acidic-group,
In said hydrolyzed process, the mass ratio containing acyl fluorides end group product that deionized water and steps A obtain controls at 1.8:1.
(C) the fluorochemical oligomeric compound that step B is obtained is carried out, except peroxide process, obtain and be less than an end band carboxylic acid of 1g/100g and the fluorine-containing oil-based polymer of salt thereof containing peroxy-radical;
(D) neutralize the fluorine-containing oil-based polymer that step C obtains, N-process comprises:
D.1: after the end band carboxylic acid that step C is obtained and the fluorine-containing oil-based polymer of salt thereof and deionized water mixing, stir;
D.2: D.1 prepare in material to step and add alkali metal hydroxide aqueous solution, obtain fluorine-containing surfactant finished product.
Except the preparation method that above-described embodiment 11 ~ 20 relates to, the preparation method that embodiment 1 ~ 10 is also enumerated by following examples completes.
Embodiment 21:
The present embodiment is the preparation method not containing the fluorine-containing surfactant of perfluoro caprylic acid for embodiment 1, and this preparation method is continuous prodution process, comprises the following steps:
A: perfluoroolefine, oxygen and Third monomer continuous feed under the pressure of the temperature of 0 DEG C and 0.1Mpa, obtained containing acyl fluorides end group product after photooxidation;
B: after being hydrolyzed containing acyl fluorides end group product, being separated, obtain the fluorochemical oligomeric compound of an end band carboxylic acid acidic-group;
C: the fluorochemical oligomeric compound obtained in step B, after salify configuration, obtains fluorine-containing surfactant finished product,
In the present embodiment, Third monomer is chloroacetylene.
Embodiment 22:
The present embodiment is the preparation method not containing the fluorine-containing surfactant of perfluoro caprylic acid for embodiment 2, and this preparation method is continuous prodution process, comprises the following steps:
A: perfluoroolefine, oxygen and Third monomer continuous feed under the pressure of the temperature of 20 DEG C and 0.5Mpa, obtained containing acyl fluorides end group product after photooxidation;
B: after being hydrolyzed containing acyl fluorides end group product, being separated, obtain the fluorochemical oligomeric compound of an end band carboxylic acid acidic-group;
C: the fluorochemical oligomeric compound obtained in step B, after salify configuration, obtains fluorine-containing surfactant finished product,
In the present embodiment, Third monomer is vinylidene.
Embodiment 23:
The present embodiment is the preparation method not containing the fluorine-containing surfactant of perfluoro caprylic acid for embodiment 3, the difference of this preparation method and embodiment 21 is: in the steps A that the present embodiment relates to, the mixed material of perfluoroolefine, oxygen and Third monomer composition completes photooxidation reaction under UV-irradiation, keep the lasting charging of mixed material and the prolonged exposure of ultraviolet light, after the perfluoroolefine that gas-liquid separation is reclaimed in product, obtain containing acyl fluorides end group product.
In the present embodiment, the charging rate of mixed material controls at 1L/H; Ultraviolet lamp is UVLED lamp, and irradiation power controls at 1W, and selection wavelength is 300nm; The mass ratio of perfluoroolefine and Third monomer is 1:1.
Embodiment 24:
The present embodiment is the preparation method not containing the fluorine-containing surfactant of perfluoro caprylic acid for embodiment 4, the difference of this preparation method and embodiment 22 is: in the steps A that the present embodiment relates to, the mixed material of perfluoroolefine, oxygen and Third monomer composition completes photooxidation reaction under UV-irradiation, keep the lasting charging of mixed material and the prolonged exposure of ultraviolet light, after the perfluoroolefine that gas-liquid separation is reclaimed in product, obtain containing acyl fluorides end group product.
In the present embodiment, the charging rate of mixed material controls at 100L/H; Ultraviolet lamp is UVLED lamp, and irradiation power controls at 100W, and selection wavelength is 410nm; The mass ratio of perfluoroolefine and Third monomer is 10:1.
Embodiment 25:
The present embodiment is the preparation method not containing the fluorine-containing surfactant of perfluoro caprylic acid for embodiment 5, the difference of this preparation method and embodiment 21 is: in the step B that the present embodiment relates to, be hydrolyzed containing adding deionized water in acyl fluorides end group product, what maintenance was hydrolyzed continues to carry out, be separated after removing gas in hydrolysate and water, obtain the fluorochemical oligomeric compound of an end band carboxylic acid acidic-group.
In the present embodiment, deionized water controls at 1:1 with the mass ratio containing acyl fluorides end group product.
Embodiment 26:
The present embodiment is the preparation method not containing the fluorine-containing surfactant of perfluoro caprylic acid for embodiment 6, the difference of this preparation method and embodiment 22 is: in the step B that the present embodiment relates to, be hydrolyzed containing adding deionized water in acyl fluorides end group product, what maintenance was hydrolyzed continues to carry out, be separated after removing gas in hydrolysate and water, obtain the fluorochemical oligomeric compound of an end band carboxylic acid acidic-group.
In the present embodiment, deionized water controls at 5:1 with the mass ratio containing acyl fluorides end group product.
Embodiment 27:
The present embodiment is the preparation method not containing the fluorine-containing surfactant of perfluoro caprylic acid for embodiment 7, and the difference of this preparation method and embodiment 21 is: in the step C that the present embodiment relates to, and salify configuration comprises the following steps:
C.1: the fluorochemical oligomeric compound of the end band carboxylic acid acidic-group that step B obtains is washed and after water-oil separating, obtains fluorochemical polyether carboxylic acid semi-finished product;
C.2: refine fluorochemical polyether carboxylic acid semi-finished product, comprise preheating and de-low process, obtain fluorochemical polyether carboxylic acid finished product, preheat temperature controls at 180 DEG C, and the molecular weight of de-low rear fluorochemical polyether carboxylic acid finished product controls 100;
C.3: in fluorochemical polyether carboxylic acid finished product and after, obtained fluorochemical polyether surfactant finished product, neutralization is the process adding alkaline, inorganic salts and deionized water in fluorochemical polyether carboxylic acid finished product, wherein, the mass ratio of fluorochemical polyether carboxylic acid finished product, alkaline, inorganic salts, deionized water is 20:5:10, and alkaline, inorganic salts can select ammonium salt.
Embodiment 28:
The present embodiment is the preparation method not containing the fluorine-containing surfactant of perfluoro caprylic acid for embodiment 8, and this preparation method is continuous prodution process, comprises the following steps:
(A) mixed material that forms of perfluoroolefine, oxygen and Third monomer (as vinyl chloride) continuous feed under the pressure of the temperature of 15 DEG C and 0.2Mpa, photooxidation reaction is completed under UV-irradiation, keep the lasting charging of mixed material and the prolonged exposure of ultraviolet light, after the perfluoroolefine that gas-liquid separation is reclaimed in product, obtain containing acyl fluorides end group product, wherein, the charging rate of mixed material controls at 20L/H; Ultraviolet lamp is UVLED lamp, and irradiation power controls at 50W, and selection wavelength is 350nm; The mass ratio of perfluoroolefine, oxygen and Third monomer is 100:100:1.
(B) be hydrolyzed containing adding deionized water in acyl fluorides end group product, keep hydrolysis continue carry out, be separated after removing gas in hydrolysate and water, obtain the fluorochemical oligomeric compound of an end band carboxylic acid acidic-group.After the hydrolysis of acyl fluorides end group product, being separated, obtain the fluorochemical oligomeric compound of an end band carboxylic acid acidic-group, wherein, deionized water controls at 1.5:1 with the mass ratio containing acyl fluorides end group product.
(C) the fluorochemical oligomeric compound obtained in step B, after salify configuration, obtains fluorine-containing surfactant finished product, and salify configuration comprises:
C.1: the fluorochemical oligomeric compound of the end band carboxylic acid acidic-group that step B obtains is washed and after water-oil separating, obtains fluorochemical polyether carboxylic acid semi-finished product;
C.2: refine fluorochemical polyether carboxylic acid semi-finished product, comprise preheating and de-low process, obtain fluorochemical polyether carboxylic acid finished product, preheat temperature controls at 220 DEG C, and the molecular weight of de-low rear fluorochemical polyether carboxylic acid finished product controls 300;
C.3: in fluorochemical polyether carboxylic acid finished product and after, obtained fluorochemical polyether surfactant finished product, neutralization is the process adding alkaline, inorganic salts and deionized water in fluorochemical polyether carboxylic acid finished product, wherein, the mass ratio of fluorochemical polyether carboxylic acid finished product, alkaline, inorganic salts, deionized water is 30:10:30, alkaline, inorganic salts can select the mixture of sodium salt and sylvite composition, and wherein, the mass ratio of sodium salt and sylvite is 1:1.
Embodiment 29:
The present embodiment is the preparation method not containing the fluorine-containing surfactant of perfluoro caprylic acid for embodiment 9, and this preparation method is continuous prodution process, comprises the following steps:
(A) mixed material that forms of perfluoroolefine, oxygen and Third monomer (as chloroacetylene) continuous feed under the pressure of the temperature of 16 DEG C and 0.4Mpa, photooxidation reaction is completed under UV-irradiation, keep the lasting charging of mixed material and the prolonged exposure of ultraviolet light, after the perfluoroolefine that gas-liquid separation is reclaimed in product, obtain containing acyl fluorides end group product, wherein, the charging rate of mixed material controls at 80L/H; Ultraviolet lamp is UVLED lamp, and irradiation power controls at 60W, and selection wavelength is 400nm; The mass ratio of perfluoroolefine, oxygen and Third monomer is 1:1:1.
(B) be hydrolyzed containing adding deionized water in acyl fluorides end group product, keep hydrolysis continue carry out, be separated after removing gas in hydrolysate and water, obtain the fluorochemical oligomeric compound of an end band carboxylic acid acidic-group.After the hydrolysis of acyl fluorides end group product, being separated, obtain the fluorochemical oligomeric compound of an end band carboxylic acid acidic-group, wherein, deionized water controls at 2:1 with the mass ratio containing acyl fluorides end group product.
(C) the fluorochemical oligomeric compound obtained in step B, after salify configuration, obtains fluorine-containing surfactant finished product, and salify configuration comprises:
C.1: the fluorochemical oligomeric compound of the end band carboxylic acid acidic-group that step B obtains is washed and after water-oil separating, obtains fluorochemical polyether carboxylic acid semi-finished product;
C.2: refine fluorochemical polyether carboxylic acid semi-finished product, comprise preheating and de-low process, obtain fluorochemical polyether carboxylic acid finished product, preheat temperature controls at 200 DEG C, and the molecular weight of de-low rear fluorochemical polyether carboxylic acid finished product controls 200;
C.3: in fluorochemical polyether carboxylic acid finished product and after, obtained fluorochemical polyether surfactant finished product, neutralization is the process adding alkaline, inorganic salts and deionized water in fluorochemical polyether carboxylic acid finished product, wherein, the mass ratio of fluorochemical polyether carboxylic acid finished product, alkaline, inorganic salts, deionized water is 25:8:20, the mixture that alkaline, inorganic salts can select ammonium salt, sodium salt and sylvite to form, wherein, the mass ratio of ammonium salt, sodium salt and sylvite is 2:3:1.
Embodiment 30:
The present embodiment is the preparation method not containing the fluorine-containing surfactant of perfluoro caprylic acid for embodiment 10, and this preparation method is continuous prodution process, comprises the following steps:
(A) mixed material that forms of perfluoroolefine, oxygen and Third monomer (as vinylidene) continuous feed under the pressure of the temperature of 10 DEG C and 0.25Mpa, photooxidation reaction is completed under UV-irradiation, keep the lasting charging of mixed material and the prolonged exposure of ultraviolet light, after the perfluoroolefine that gas-liquid separation is reclaimed in product, obtain containing acyl fluorides end group product, wherein, the charging rate of mixed material controls at 45L/H; Ultraviolet lamp is UVLED lamp, and irradiation power controls at 85W, and selection wavelength is 390nm; The mass ratio of perfluoroolefine, oxygen and Third monomer is 80:90:1.
(B) be hydrolyzed containing adding deionized water in acyl fluorides end group product, keep hydrolysis continue carry out, be separated after removing gas in hydrolysate and water, obtain the fluorochemical oligomeric compound of an end band carboxylic acid acidic-group.After the hydrolysis of acyl fluorides end group product, being separated, obtain the fluorochemical oligomeric compound of an end band carboxylic acid acidic-group, wherein, deionized water controls at 1.6:1 with the mass ratio containing acyl fluorides end group product.
(C) the fluorochemical oligomeric compound obtained in step B, after salify configuration, obtains fluorine-containing surfactant finished product, and salify configuration comprises:
C.1: the fluorochemical oligomeric compound of the end band carboxylic acid acidic-group that step B obtains is washed and after water-oil separating, obtains fluorochemical polyether carboxylic acid semi-finished product;
C.2: refine fluorochemical polyether carboxylic acid semi-finished product, comprise preheating and de-low process, obtain fluorochemical polyether carboxylic acid finished product, preheat temperature controls at 200 DEG C, and the molecular weight of de-low rear fluorochemical polyether carboxylic acid finished product controls 260;
C.3: in fluorochemical polyether carboxylic acid finished product and after, obtained fluorochemical polyether surfactant finished product, neutralization is the process adding alkaline, inorganic salts and deionized water in fluorochemical polyether carboxylic acid finished product, wherein, the mass ratio of fluorochemical polyether carboxylic acid finished product, alkaline, inorganic salts, deionized water is 12:8:27, and alkaline, inorganic salts can select sylvite.
For adapting to suitability for industrialized production of the present invention, illustrate the industrial production system in embodiment 11 ~ 20 involved by preparation method with several exemplary embodiments below.
Embodiment 31:
So the present embodiment is the process system not containing the fluorine-containing surfactant of perfluoro caprylic acid with the preparation of embodiment 11, in the present embodiment, process system comprises the photooxidation reaction device, hydrolytic reaction pot, heat treatment reactor and the neutralization reaction still that are communicated with successively, photooxidation reaction device is connected to perfluoroolefine storage tank and breather pipe, breather pipe is the water sealing (sealing water) pipe passing into mist in photooxidation reaction device, mist is made up of oxygen and Third monomer, and neutralization reaction still is connected with the finished product storage tank storing fluorochemical polyether surfactant.
Embodiment 32:
So the present embodiment is the process system not containing the fluorine-containing surfactant of perfluoro caprylic acid with the preparation of embodiment 12, the difference of this process system and embodiment 31 is: the photooxidation reaction device that the present embodiment relates to is provided with the stainless steel equipment of quartzy sheath and thermocouple in being, described quartzy sheath to be evenly distributed on centered by photooxidation reaction device axis circumferentially, and be provided with two-layer from inside to outside along photooxidation reaction device axis, described photooxidation reaction device is provided with exhaust outlet.
Embodiment 33:
So the present embodiment is the process system not containing the fluorine-containing surfactant of perfluoro caprylic acid with the preparation of embodiment 13, the difference of this process system and embodiment 31 is: the present embodiment is provided with reflux condensing tube on photooxidation reaction device, perfluoroolefine from perfluoroolefine storage tank is sent in photooxidation reaction device through reflux condensing tube, and the condensation temperature of reflux condensing tube is-30 DEG C.
Embodiment 34:
So the present embodiment is the process system not containing the fluorine-containing surfactant of perfluoro caprylic acid with the preparation of embodiment 14, the difference of this process system and embodiment 31 is: the hydrolytic reaction pot that the present embodiment relates to is the consersion unit that carbon steel lining fluorine or carbon steel spray polytetrafluoro coating, hydrolytic reaction pot is provided with the liquid phase charge door, evacuation port and the cooling jacket that add for photooxidation reaction product and deionized water, in hydrolytic reaction pot, is provided with agitator.
Embodiment 35:
So the present embodiment is the process system not containing the fluorine-containing surfactant of perfluoro caprylic acid with the preparation of embodiment 15, the difference of this process system and embodiment 31 is: the heat treatment reactor that the present embodiment relates to is the consersion unit of carbon steel lining fluorine or carbon steel polytetrafluoroethylene spray, and described heat treatment reactor is provided with agitator, heating inner coil pipe, heating jacket, conduction oil device.
Embodiment 36:
The present embodiment is containing the process system of fluorine-containing surfactant of perfluoro caprylic acid for the preparation of embodiment 16, the difference of this process system and embodiment 31 is: the neutralization reaction still that the present embodiment relates to is stainless steel cauldron, neutralization reaction still is provided with the charge door and cooling water jecket that add for alkaline solution and deionized water, in neutralization reaction still, is provided with agitator.
Embodiment 37:
So the present embodiment is the process system not containing the fluorine-containing surfactant of perfluoro caprylic acid with the preparation of embodiment 17, this process system flow process is as follows:
(A) at the temperature of-20 DEG C, perfluoroolefine is added in photooxidation reaction device, the mist that oxygen and Third monomer (as chloroacetylene) form is passed in photooxidation reaction device, ultraviolet lamp irradiation and duration of ventilation is kept to be after 2h, close ultraviolet lamp, exhaust, unreacted perfluoroolefine is reclaimed after room temprature evaporation, obtained containing acyl fluorides end group product.In above process, perfluoroolefine, the mass ratio of oxygen and Third monomer is 100:100:1, photooxidation reaction device is provided with the stainless steel equipment of quartzy sheath and thermocouple in selecting, quartz sheath to be evenly distributed on centered by photooxidation reaction device axis circumferentially, and be provided with two-layer from inside to outside along photooxidation reaction device axis, photooxidation reaction device is provided with exhaust outlet and reflux condensing tube, perfluoroolefine from perfluoroolefine storage tank is sent in photooxidation reaction device through reflux condensing tube, the condensation temperature of reflux condensing tube controls at-60 DEG C, UV-irradiation power in quartz sheath controls at 100W, selection wavelength is 305nm.
(B) B.1: add in hydrolytic reaction pot deionized water and steps A obtained containing acyl fluorides end group product, be uniformly mixed;
B.2: the temperature that B.1 rate-determining steps prepares liquid phase fluid in material is 30 DEG C, continue to add in hydrolytic reaction pot steps A obtained containing acyl fluorides end group product, adding speed is 1L/H, and mixing time controls at 0.5h;
B.3: stir after stopping, static layering, after removing upper water, obtain the fluorochemical oligomeric compound of an end band carboxylic acid acidic-group.
In above process, the mass ratio containing acyl fluorides end group product that deionized water and steps A obtain is 1.5:1, hydrolytic reaction pot selects the consersion unit of carbon steel lining fluorine or carbon steel spraying polytetrafluoro coating, hydrolytic reaction pot is provided with the liquid phase charge door, evacuation port and the cooling jacket that add containing acyl fluorides end group product and deionized water that obtain for steps A, in hydrolytic reaction pot, is provided with agitator.
(C) fluorochemical oligomeric compound obtained for step B is sent into heat treatment reactor, an end band carboxylic acid of 1g/100g and the fluorine-containing oil-based polymer of salt thereof is less than containing peroxy-radical through obtaining after peroxide process, wherein, the consersion unit of carbon steel lining fluorine or carbon steel polytetrafluoroethylene spray selected by heat treatment reactor, and heat treatment reactor is provided with agitator, heating inner coil pipe, heating jacket, conduction oil device.
(D) D.1: in neutralization reaction still, add an end band carboxylic acid that step C obtains and salt thereof fluorine-containing oil-based polymer and deionized water, mix and stir;
D.2: D.1 prepare in material to step and add alkali metal hydroxide aqueous solution, obtain fluorine-containing surfactant finished product, send into finished product storage tank to store.
In above process, neutralization reaction still can select stainless steel cauldron, neutralization reaction still is provided with the charge door and cooling water jecket that add for alkaline solution and deionized water, in neutralization reaction still, is provided with agitator.
Embodiment 38:
So the present embodiment is the process system not containing the fluorine-containing surfactant of perfluoro caprylic acid with the preparation of embodiment 18, this process system flow process is as follows:
(A) at the temperature of-25 DEG C, perfluoroolefine is added in photooxidation reaction device, the mist that oxygen and Third monomer (as vinyl chloride) form is passed in photooxidation reaction device, ultraviolet lamp irradiation and duration of ventilation is kept to be after 20h, close ultraviolet lamp, exhaust, unreacted perfluoroolefine is reclaimed after room temprature evaporation, obtained containing acyl fluorides end group product.In above process, perfluoroolefine, the mass ratio of oxygen and Third monomer is 1:1:1, photooxidation reaction device is provided with the stainless steel equipment of quartzy sheath and thermocouple in selecting, quartz sheath to be evenly distributed on centered by photooxidation reaction device axis circumferentially, and be provided with two-layer from inside to outside along photooxidation reaction device axis, photooxidation reaction device is provided with exhaust outlet and reflux condensing tube, perfluoroolefine from perfluoroolefine storage tank is sent in photooxidation reaction device through reflux condensing tube, the condensation temperature of reflux condensing tube controls at-40 DEG C, UV-irradiation power in quartz sheath controls at 1000W, selection wavelength is 420nm.
(B) B.1: add in hydrolytic reaction pot deionized water and steps A obtained containing acyl fluorides end group product, be uniformly mixed;
B.2: the temperature that B.1 rate-determining steps prepares liquid phase fluid in material is 50 DEG C, continue to add in hydrolytic reaction pot steps A obtained containing acyl fluorides end group product, adding speed is 100L/H, and mixing time controls at 5h;
B.3: stir after stopping, static layering, after removing upper water, obtain the fluorochemical oligomeric compound of an end band carboxylic acid acidic-group.
In above process, the mass ratio containing acyl fluorides end group product that deionized water and steps A obtain is 2:1, hydrolytic reaction pot selects the consersion unit of carbon steel lining fluorine or carbon steel spraying polytetrafluoro coating, hydrolytic reaction pot is provided with the liquid phase charge door, evacuation port and the cooling jacket that add containing acyl fluorides end group product and deionized water that obtain for steps A, in hydrolytic reaction pot, is provided with agitator.
(C) fluorochemical oligomeric compound obtained for step B is sent into heat treatment reactor, an end band carboxylic acid of 1g/100g and the fluorine-containing oil-based polymer of salt thereof is less than containing peroxy-radical through obtaining after peroxide process, wherein, the consersion unit of carbon steel lining fluorine or carbon steel polytetrafluoroethylene spray selected by heat treatment reactor, and heat treatment reactor is provided with agitator, heating inner coil pipe, heating jacket, conduction oil device.
(D) D.1: in neutralization reaction still, add an end band carboxylic acid that step C obtains and salt thereof fluorine-containing oil-based polymer and deionized water, mix and stir;
D.2: D.1 prepare in material to step and add ammonia aqueous solution, obtain fluorine-containing surfactant finished product, send into finished product storage tank to store.
In above process, neutralization reaction still can select stainless steel cauldron, neutralization reaction still is provided with the charge door and cooling water jecket that add for alkaline solution and deionized water, in neutralization reaction still, is provided with agitator.
Embodiment 39:
So the present embodiment is the process system not containing the fluorine-containing surfactant of perfluoro caprylic acid with the preparation of embodiment 19, this process system flow process is as follows:
(A) at the temperature of-23 DEG C, perfluoroolefine is added in photooxidation reaction device, the mist that oxygen and Third monomer (as vinylidene) form is passed in photooxidation reaction device, ultraviolet lamp irradiation and duration of ventilation is kept to be after 16h, close ultraviolet lamp, exhaust, unreacted perfluoroolefine is reclaimed after room temprature evaporation, obtained containing acyl fluorides end group product.In above process, perfluoroolefine, the mass ratio of oxygen and Third monomer is 50:80:1, photooxidation reaction device is provided with the stainless steel equipment of quartzy sheath and thermocouple in selecting, quartz sheath to be evenly distributed on centered by photooxidation reaction device axis circumferentially, and be provided with two-layer from inside to outside along photooxidation reaction device axis, photooxidation reaction device is provided with exhaust outlet and reflux condensing tube, perfluoroolefine from perfluoroolefine storage tank is sent in photooxidation reaction device through reflux condensing tube, the condensation temperature of reflux condensing tube controls at-55 DEG C, UV-irradiation power in quartz sheath controls at 800W, selection wavelength is 380nm.
(B) B.1: add in hydrolytic reaction pot deionized water and steps A obtained containing acyl fluorides end group product, be uniformly mixed;
B.2: the temperature that B.1 rate-determining steps prepares liquid phase fluid in material is 40 DEG C, continue to add in hydrolytic reaction pot steps A obtained containing acyl fluorides end group product, adding speed is 55L/H, and mixing time controls at 3.5h;
B.3: stir after stopping, static layering, after removing upper water, obtain the fluorochemical oligomeric compound of an end band carboxylic acid acidic-group.
In above process, the mass ratio containing acyl fluorides end group product that deionized water and steps A obtain is 1.6:1, hydrolytic reaction pot selects the consersion unit of carbon steel lining fluorine or carbon steel spraying polytetrafluoro coating, hydrolytic reaction pot is provided with the liquid phase charge door, evacuation port and the cooling jacket that add containing acyl fluorides end group product and deionized water that obtain for steps A, in hydrolytic reaction pot, is provided with agitator.
(C) fluorochemical oligomeric compound obtained for step B is sent into heat treatment reactor, an end band carboxylic acid of 1g/100g and the fluorine-containing oil-based polymer of salt thereof is less than containing peroxy-radical through obtaining after peroxide process, wherein, the consersion unit of carbon steel lining fluorine or carbon steel polytetrafluoroethylene spray selected by heat treatment reactor, and heat treatment reactor is provided with agitator, heating inner coil pipe, heating jacket, conduction oil device.
(D) D.1: in neutralization reaction still, add an end band carboxylic acid that step C obtains and salt thereof fluorine-containing oil-based polymer and deionized water, mix and stir;
D.2: D.1 prepare in material to step and add ammonia aqueous solution, obtain fluorine-containing surfactant finished product, send into finished product storage tank to store.
In above process, neutralization reaction still can select stainless steel cauldron, neutralization reaction still is provided with the charge door and cooling water jecket that add for alkaline solution and deionized water, in neutralization reaction still, is provided with agitator.
Embodiment 40:
So the present embodiment is the process system not containing the fluorine-containing surfactant of perfluoro caprylic acid with the preparation of embodiment 20, this process system flow process is as follows:
(A) at the temperature of-22 DEG C, perfluoroolefine is added in photooxidation reaction device, the mist that oxygen and Third monomer (as chloroacetylene) form is passed in photooxidation reaction device, ultraviolet lamp irradiation and duration of ventilation is kept to be after 10h, close ultraviolet lamp, exhaust, unreacted perfluoroolefine is reclaimed after room temprature evaporation, obtained containing acyl fluorides end group product.In above process, perfluoroolefine, the mass ratio of oxygen and Third monomer is 30:60:1, photooxidation reaction device is provided with the stainless steel equipment of quartzy sheath and thermocouple in selecting, quartz sheath to be evenly distributed on centered by photooxidation reaction device axis circumferentially, and be provided with two-layer from inside to outside along photooxidation reaction device axis, photooxidation reaction device is provided with exhaust outlet and reflux condensing tube, perfluoroolefine from perfluoroolefine storage tank is sent in photooxidation reaction device through reflux condensing tube, the condensation temperature of reflux condensing tube controls at-35 DEG C, UV-irradiation power in quartz sheath controls at 700W, selection wavelength is 320nm.
(B) B.1: add in hydrolytic reaction pot deionized water and steps A obtained containing acyl fluorides end group product, be uniformly mixed;
B.2: the temperature that B.1 rate-determining steps prepares liquid phase fluid in material is 40 DEG C, continue to add in hydrolytic reaction pot steps A obtained containing acyl fluorides end group product, adding speed is 70L/H, and mixing time controls at 4.5h;
B.3: stir after stopping, static layering, after removing upper water, obtain the fluorochemical oligomeric compound of an end band carboxylic acid acidic-group.
In above process, the mass ratio containing acyl fluorides end group product that deionized water and steps A obtain is 1.8:1, hydrolytic reaction pot selects the consersion unit of carbon steel lining fluorine or carbon steel spraying polytetrafluoro coating, hydrolytic reaction pot is provided with the liquid phase charge door, evacuation port and the cooling jacket that add containing acyl fluorides end group product and deionized water that obtain for steps A, in hydrolytic reaction pot, is provided with agitator.
(C) fluorochemical oligomeric compound obtained for step B is sent into heat treatment reactor, an end band carboxylic acid of 1g/100g and the fluorine-containing oil-based polymer of salt thereof is less than containing peroxy-radical through obtaining after peroxide process, wherein, the consersion unit of carbon steel lining fluorine or carbon steel polytetrafluoroethylene spray selected by heat treatment reactor, and heat treatment reactor is provided with agitator, heating inner coil pipe, heating jacket, conduction oil device.
(D) D.1: in neutralization reaction still, add an end band carboxylic acid that step C obtains and salt thereof fluorine-containing oil-based polymer and deionized water, mix and stir;
D.2: D.1 prepare in material to step and add alkali metal hydroxide aqueous solution, obtain fluorine-containing surfactant finished product, send into finished product storage tank to store.
In above process, neutralization reaction still can select stainless steel cauldron, neutralization reaction still is provided with the charge door and cooling water jecket that add for alkaline solution and deionized water, in neutralization reaction still, is provided with agitator.
For adapting to serialization industrial production of the present invention, illustrate the industrial production system in embodiment 21 ~ 30 involved by preparation method with several exemplary embodiments below.
Embodiment 41:
The present embodiment is containing the continuous process system of fluorine-containing surfactant of perfluoro caprylic acid for the preparation of embodiment 21, this process system comprises the photooxidation reaction loop be connected successively, hydrolysis unit and salify dispensing unit, photooxidation reaction loop comprises perfluoroolefine storage tank, Third monomer storage tank, photooxidation reaction device and gas-liquid separator, air and liquid mixer is connected with at the entrance of photooxidation reaction device, perfluoroolefine, Third monomer and oxygen send into photooxidation reaction device through air and liquid mixer, gas-liquid separator is connected in the outlet of photooxidation reaction device, the gaseous phase outlet of gas-liquid separator is connected with perfluoroolefine storage tank, the liquid-phase outlet of gas-liquid separator is connected with hydrolysis unit, salify dispensing unit is connected with the finished product storage tank storing fluorochemical polyether surfactant.
Embodiment 42:
The present embodiment is containing the continuous process system of fluorine-containing surfactant of perfluoro caprylic acid for the preparation of embodiment 22, the difference of this continuous process system and embodiment 41 is: in the present embodiment, photooxidation reaction loop also comprises the condenser of precooling reaction raw materials and precooling gas-liquid separator gas recovery, the quantity of described condenser is three groups, and one group is connected on Third monomer storage tank; One group is connected on perfluoroolefine storage tank; One group is connected between perfluoroolefine storage tank and the gaseous phase outlet of gas-liquid separator.
In the present embodiment, photooxidation reaction device is the tubular reactor be composed in series by glass tube, series connection direction along glass tube is evenly arranged the ultraviolet aperture of more than a group, often organize ultraviolet aperture to be made up of the LED uviol lamp pearl be circumferentially evenly arranged apart from glass tube external diameter 1mm, the light-emitting area of LED uviol lamp pearl is corresponding on glass tube, and the quantity of glass tube is 50, and the length of every root glass tube is 1m, the quantity of LED uviol lamp pearl is 50, and the wavelength of each LED uviol lamp pearl is 365nm.
Embodiment 43:
The present embodiment is containing the continuous process system of fluorine-containing surfactant of perfluoro caprylic acid for the preparation of embodiment 23, the difference of this continuous process system and embodiment 42 is: the hydrolysis unit that the present embodiment relates to comprises circulation, the hydrolysis reactor be connected with the liquid-phase outlet of gas-liquid separator, connect the three phase separator of hydrolysis reactor outlet, the entrance of hydrolysis reactor is all connected with circulation with the aqueous phase outlet of three phase separator, tail gas evacuation port is provided with at the gaseous phase outlet of three phase separator, the oil phase outlet of three phase separator is provided with the fluorochemical oligomeric compound storage tank be connected with salify dispensing unit.
The hydrolysis reactor that the present embodiment relates to is the tubular reactor be composed in series by steel lining resin pipeline, and the internal diameter of steel lining resin pipeline is 20mm, in hydrolysis reactor, be provided with mixing baffle.
Embodiment 44:
The present embodiment is containing the continuous process system of fluorine-containing surfactant of perfluoro caprylic acid for the preparation of embodiment 24, this continuous process system is with the difference of embodiment 43: the salify dispensing unit that the present embodiment relates to comprise be connected successively washing process, rectification flow and in and flow process, washing process comprises the washing kettle be connected with fluorochemical oligomeric compound storage tank successively, first oil water separator and the second oil water separator, washing kettle entrance, first oil water separator aqueous phase outlet, second oil water separator aqueous phase outlet is all connected with circulation, second oil water separator oil phase outlet is provided with the fluorochemical polyether carboxylic acid semi-finished product storage tank be connected with rectification flow, during finished product storage tank is connected to and in flow process.
In the present embodiment, rectification flow comprises the preheater that is connected with fluorochemical polyether carboxylic acid semi-finished product storage tank successively and de-low device, described de-low device is provided with in the fluorochemical polyether carboxylic acid finished product storage tank that is connected with flow process and evacuation port.
In and flow process comprise in and batch tank, in and batch tank entrance be connected with alkali lye batch tank and pure water batch tank, in and batch tank export be connected finished product batch tank.
Embodiment 45:
The present embodiment is that the difference of this continuous process system and embodiment 44 is for the preparation of embodiment 25 containing the continuous process system of fluorine-containing surfactant of perfluoro caprylic acid: the present embodiment is at preheater and take off on low device and be all connected with the heat-conducting oil system providing thermal source.
Embodiment 46:
The present embodiment is that the difference of this continuous process system and embodiment 44 is: the present embodiment is all connected with the freezing liquid circulatory system of control temperature on photooxidation reaction device, condenser, Third monomer storage tank, perfluoroolefine storage tank, hydrolysis reactor for the preparation of embodiment 26 containing the continuous process system of fluorine-containing surfactant of perfluoro caprylic acid.
Embodiment 47:
The present embodiment is containing the continuous process system of fluorine-containing surfactant of perfluoro caprylic acid for the preparation of embodiment 27, this continuous process system is with the difference of embodiment 44: on the condenser being connected gas-liquid separator gaseous phase outlet and perfluoroolefine storage tank, be provided with offgas outlet, offgas outlet, tail gas evacuation port and evacuation port is connected with the tail gas purification tower of process tail gas.
Embodiment 48:
So the present embodiment is the continuous process system not containing the fluorine-containing surfactant of perfluoro caprylic acid with the preparation of embodiment 28, this continuous process system flow is as follows:
(A) perfluoroolefine, oxygen and Third monomer (as vinylidene) enter photooxidation reaction loop continuously under the pressure of the temperature of 0 DEG C and 0.1Mpa, obtained containing acyl fluorides end group product after photooxidation, wherein, photooxidation loop comprises perfluoroolefine storage tank, Third monomer storage tank, photooxidation reaction device, gas-liquid separator and air and liquid mixer.In above-mentioned steps, from the perfluoroolefine of perfluoroolefine storage tank, oxygen with to be formed after mixed material through air and liquid mixer from the perfluoroolefine of Third monomer storage tank and send into photooxidation reaction device, photooxidation reaction is completed under UV-irradiation, keep the lasting charging of mixed material and the prolonged exposure of ultraviolet light, product sends into gas-liquid separator continuously, be separated the unreacted perfluoroolefine that obtains and containing acyl fluorides end group product, unreacted perfluoroolefine sends into perfluoroolefine storage tank, sends into hydrolysis unit containing acyl fluorides end group product.
In the present embodiment, the mass ratio of perfluoroolefine, oxygen and Third monomer is 50:100:1; Photooxidation reaction device is the tubular reactor be composed in series by glass tube, series connection direction along glass tube is evenly arranged the ultraviolet aperture of more than a group, often organize ultraviolet aperture to be made up of the LED uviol lamp pearl be circumferentially evenly arranged apart from glass tube external diameter 5mm, the light-emitting area of LED uviol lamp pearl is corresponding on glass tube.Wherein, the quantity of glass tube is 100, and the length of every root glass tube is 2m; The quantity of LED uviol lamp pearl is 100, and the wavelength of each LED uviol lamp pearl is 405nm.
Photooxidation loop also condenser, the quantity of condenser is three groups, and one group is connected on Third monomer storage tank; One group is connected on perfluoroolefine storage tank; One group is connected between perfluoroolefine storage tank and the gaseous phase outlet of gas-liquid separator.
(B) will send into hydrolysis unit containing acyl fluorides end group product, after hydrolysis, separation, obtain the fluorochemical oligomeric compound of an end band carboxylic acid acidic-group, wherein, hydrolysis unit comprises circulation, hydrolysis reactor and three phase separator.In above-mentioned steps, add in hydrolysis reactor containing acyl fluorides end group product, system water is added to hydrolysis reactor by circulation, what maintenance was hydrolyzed continues to carry out, hydrolysate sends into three phase separator continuously, and be separated the fluorochemical oligomeric compound obtaining acid tail gas, water and an end band carboxylic acid acidic-group, acid tail gas is discharged by the tail gas evacuation port of three phase separator, water returns circulation, and the fluorochemical oligomeric compound of an end band carboxylic acid acidic-group sends into salify dispensing unit.
In the present embodiment, system water is 1.5:1 with the mass ratio containing acyl fluorides end group product; Hydrolysis reactor is the tubular reactor be composed in series by steel lining resin pipeline, and the internal diameter of steel lining resin pipeline is 20mm, in hydrolysis reactor, be provided with mixing baffle.
(C) the fluorochemical oligomeric compound of an end band carboxylic acid acidic-group obtained in step B is sent into salify dispensing unit, salify dispensing unit comprise washing process, rectification flow and in and flow process, comprise the following steps:
C.1: the fluorochemical oligomeric compound of the end band carboxylic acid acidic-group obtained by step B sends into washing process, washing process comprises: the fluorochemical oligomeric compound of the end band carboxylic acid acidic-group obtained by step B sends into washing kettle, circulation is to washing kettle supply system water, oil water separator is sent into after washing, separation obtains water and fluorochemical polyether carboxylic acid semi-finished product, water returns circulation, and fluorochemical polyether carboxylic acid semi-finished product send into rectification flow;
C.2: fluorochemical polyether carboxylic acid semi-finished product are sent into rectification flow, rectification flow comprises: fluorochemical polyether carboxylic acid semi-finished product are sent into preheater successively, de-low device is sent into after the preheating temperature of 180 DEG C, fluorochemical polyether carboxylic acid finished product is obtained after de-low, its molecular weight controls 100, and preheater and de-low device are all connected with the heat-conducting oil system providing thermal source;
C.3: by fluorochemical polyether carboxylic acid finished product send in and flow process, in and flow process comprise: by fluorochemical polyether carboxylic acid finished product send in and preparing tank, to in and preparing tank in add alkali lye and pure water after, obtain fluorochemical polyether surfactant finished product, this fluorine-containing surfactant finished product is sent into finished product storage tank and is stored.Count in mass ratio, fluorochemical polyether carboxylic acid finished product: alkali lye: pure water=20:5:10, alkali lye is ammonium salt.
For improving the industrial usability of the present embodiment further, between three phase separator and washing kettle, between oil water separator and preheater, de-low device and in and be equipped with intermediate storage tank between preparing tank; Photooxidation reaction device, condenser, Third monomer storage tank, perfluoroolefine storage tank, hydrolysis reactor are all connected with the freezing liquid circulatory system of control temperature; De-low device is provided with evacuation port, the condenser connecting gas-liquid separator gaseous phase outlet and perfluoroolefine storage tank is provided with offgas outlet, offgas outlet, tail gas evacuation port and evacuation port is connected with the tail gas purification tower of process tail gas.
Embodiment 49:
So the present embodiment is the continuous process system not containing the fluorine-containing surfactant of perfluoro caprylic acid with the preparation of embodiment 29, this continuous process system flow is as follows:
(A) perfluoroolefine, oxygen and Third monomer (as chloroacetylene) enter photooxidation reaction loop continuously under the pressure of the temperature of 20 DEG C and 0.5Mpa, obtained containing acyl fluorides end group product after photooxidation, wherein, photooxidation loop comprises perfluoroolefine storage tank, Third monomer storage tank, photooxidation reaction device, gas-liquid separator and air and liquid mixer.In above-mentioned steps, from the perfluoroolefine of perfluoroolefine storage tank, oxygen with to be formed after mixed material through air and liquid mixer from the perfluoroolefine of Third monomer storage tank and send into photooxidation reaction device, photooxidation reaction is completed under UV-irradiation, keep the lasting charging of mixed material and the prolonged exposure of ultraviolet light, product sends into gas-liquid separator continuously, be separated the unreacted perfluoroolefine that obtains and containing acyl fluorides end group product, unreacted perfluoroolefine sends into perfluoroolefine storage tank, sends into hydrolysis unit containing acyl fluorides end group product.
In the present embodiment, the mass ratio of perfluoroolefine, oxygen and Third monomer is 1:1:1; Photooxidation reaction device is the tubular reactor be composed in series by glass tube, series connection direction along glass tube is evenly arranged the ultraviolet aperture of more than a group, often organize ultraviolet aperture to be made up of the LED uviol lamp pearl be circumferentially evenly arranged apart from glass tube external diameter 3mm, the light-emitting area of LED uviol lamp pearl is corresponding on glass tube.Wherein, the quantity of glass tube is 80, and the length of every root glass tube is 1.5m; The quantity of LED uviol lamp pearl is 60, and the wavelength of each LED uviol lamp pearl is 388nm.
Photooxidation loop also condenser, the quantity of condenser is three groups, and one group is connected on Third monomer storage tank; One group is connected on perfluoroolefine storage tank; One group is connected between perfluoroolefine storage tank and the gaseous phase outlet of gas-liquid separator.
(B) will send into hydrolysis unit containing acyl fluorides end group product, after hydrolysis, separation, obtain the fluorochemical oligomeric compound of an end band carboxylic acid acidic-group, wherein, hydrolysis unit comprises circulation, hydrolysis reactor and three phase separator.In above-mentioned steps, add in hydrolysis reactor containing acyl fluorides end group product, system water is added to hydrolysis reactor by circulation, what maintenance was hydrolyzed continues to carry out, hydrolysate sends into three phase separator continuously, and be separated the fluorochemical oligomeric compound obtaining acid tail gas, water and an end band carboxylic acid acidic-group, acid tail gas is discharged by the tail gas evacuation port of three phase separator, water returns circulation, and the fluorochemical oligomeric compound of an end band carboxylic acid acidic-group sends into salify dispensing unit.
In the present embodiment, system water is 2:1 with the mass ratio containing acyl fluorides end group product; Hydrolysis reactor is the tubular reactor be composed in series by steel lining resin pipeline, and the internal diameter of steel lining resin pipeline is 40mm, in hydrolysis reactor, be provided with mixing baffle.
(C) the fluorochemical oligomeric compound of an end band carboxylic acid acidic-group obtained in step B is sent into salify dispensing unit, salify dispensing unit comprise washing process, rectification flow and in and flow process, comprise the following steps:
C.1: the fluorochemical oligomeric compound of the end band carboxylic acid acidic-group obtained by step B sends into washing process, washing process comprises: the fluorochemical oligomeric compound of the end band carboxylic acid acidic-group obtained by step B sends into washing kettle, circulation is to washing kettle supply system water, oil water separator is sent into after washing, separation obtains water and fluorochemical polyether carboxylic acid semi-finished product, water returns circulation, and fluorochemical polyether carboxylic acid semi-finished product send into rectification flow;
C.2: fluorochemical polyether carboxylic acid semi-finished product are sent into rectification flow, rectification flow comprises: fluorochemical polyether carboxylic acid semi-finished product are sent into preheater successively, de-low device is sent into after the preheating temperature of 220 DEG C, fluorochemical polyether carboxylic acid finished product is obtained after de-low, its molecular weight controls 300, and preheater and de-low device are all connected with the heat-conducting oil system providing thermal source;
C.3: by fluorochemical polyether carboxylic acid finished product send in and flow process, in and flow process comprise: by fluorochemical polyether carboxylic acid finished product send in and preparing tank, to in and preparing tank in add alkali lye and pure water after, obtain fluorochemical polyether surfactant finished product, this fluorine-containing surfactant finished product is sent into finished product storage tank and is stored.Count in mass ratio, fluorochemical polyether carboxylic acid finished product: alkali lye: pure water=30:10:30, alkali lye is sylvite.
For improving the industrial usability of the present embodiment further, between three phase separator and washing kettle, between oil water separator and preheater, de-low device and in and be equipped with intermediate storage tank between preparing tank; Photooxidation reaction device, condenser, Third monomer storage tank, perfluoroolefine storage tank, hydrolysis reactor are all connected with the freezing liquid circulatory system of control temperature; De-low device is provided with evacuation port, the condenser connecting gas-liquid separator gaseous phase outlet and perfluoroolefine storage tank is provided with offgas outlet, offgas outlet, tail gas evacuation port and evacuation port is connected with the tail gas purification tower of process tail gas.
Embodiment 50:
So the present embodiment is the continuous process system not containing the fluorine-containing surfactant of perfluoro caprylic acid with the preparation of embodiment 30, this continuous process system flow is as follows:
(A) perfluoroolefine, oxygen and Third monomer (as vinylidene) enter photooxidation reaction loop continuously under the pressure of the temperature of 12 DEG C and 0.3Mpa, obtained containing acyl fluorides end group product after photooxidation, wherein, photooxidation loop comprises perfluoroolefine storage tank, Third monomer storage tank, photooxidation reaction device, gas-liquid separator and air and liquid mixer.In above-mentioned steps, from the perfluoroolefine of perfluoroolefine storage tank, oxygen with to be formed after mixed material through air and liquid mixer from the perfluoroolefine of Third monomer storage tank and send into photooxidation reaction device, photooxidation reaction is completed under UV-irradiation, keep the lasting charging of mixed material and the prolonged exposure of ultraviolet light, product sends into gas-liquid separator continuously, be separated the unreacted perfluoroolefine that obtains and containing acyl fluorides end group product, unreacted perfluoroolefine sends into perfluoroolefine storage tank, sends into hydrolysis unit containing acyl fluorides end group product.
In the present embodiment, the mass ratio of perfluoroolefine, oxygen and Third monomer is 100:50:1; Photooxidation reaction device is the tubular reactor be composed in series by glass tube, series connection direction along glass tube is evenly arranged the ultraviolet aperture of more than a group, often organize ultraviolet aperture to be made up of the LED uviol lamp pearl be circumferentially evenly arranged apart from glass tube external diameter 3mm, the light-emitting area of LED uviol lamp pearl is corresponding on glass tube.Wherein, the quantity of glass tube is 80, and the length of every root glass tube is 1.8m; The quantity of LED uviol lamp pearl is 60, and the wavelength of each LED uviol lamp pearl is 400nm.
Photooxidation loop also condenser, the quantity of condenser is three groups, and one group is connected on Third monomer storage tank; One group is connected on perfluoroolefine storage tank; One group is connected between perfluoroolefine storage tank and the gaseous phase outlet of gas-liquid separator.
(B) will send into hydrolysis unit containing acyl fluorides end group product, after hydrolysis, separation, obtain the fluorochemical oligomeric compound of an end band carboxylic acid acidic-group, wherein, hydrolysis unit comprises circulation, hydrolysis reactor and three phase separator.In above-mentioned steps, add in hydrolysis reactor containing acyl fluorides end group product, system water is added to hydrolysis reactor by circulation, what maintenance was hydrolyzed continues to carry out, hydrolysate sends into three phase separator continuously, and be separated the fluorochemical oligomeric compound obtaining acid tail gas, water and an end band carboxylic acid acidic-group, acid tail gas is discharged by the tail gas evacuation port of three phase separator, water returns circulation, and the fluorochemical oligomeric compound of an end band carboxylic acid acidic-group sends into salify dispensing unit.
In the present embodiment, system water is 1.7:1 with the mass ratio containing acyl fluorides end group product; Hydrolysis reactor is the tubular reactor be composed in series by steel lining resin pipeline, and the internal diameter of steel lining resin pipeline is 38mm, in hydrolysis reactor, be provided with mixing baffle.
(C) the fluorochemical oligomeric compound of an end band carboxylic acid acidic-group obtained in step B is sent into salify dispensing unit, salify dispensing unit comprise washing process, rectification flow and in and flow process, comprise the following steps:
C.1: the fluorochemical oligomeric compound of the end band carboxylic acid acidic-group obtained by step B sends into washing process, washing process comprises: the fluorochemical oligomeric compound of the end band carboxylic acid acidic-group obtained by step B sends into washing kettle, circulation is to washing kettle supply system water, oil water separator is sent into after washing, separation obtains water and fluorochemical polyether carboxylic acid semi-finished product, water returns circulation, and fluorochemical polyether carboxylic acid semi-finished product send into rectification flow;
C.2: fluorochemical polyether carboxylic acid semi-finished product are sent into rectification flow, rectification flow comprises: fluorochemical polyether carboxylic acid semi-finished product are sent into preheater successively, de-low device is sent into after the preheating temperature of 200 DEG C, fluorochemical polyether carboxylic acid finished product is obtained after de-low, its molecular weight controls 280, and preheater and de-low device are all connected with the heat-conducting oil system providing thermal source;
C.3: by fluorochemical polyether carboxylic acid finished product send in and flow process, in and flow process comprise: by fluorochemical polyether carboxylic acid finished product send in and preparing tank, to in and preparing tank in add alkali lye and pure water after, obtain fluorochemical polyether surfactant finished product, this fluorine-containing surfactant finished product is sent into finished product storage tank and is stored.Count in mass ratio, fluorochemical polyether carboxylic acid finished product: alkali lye: pure water=16:7:15, alkali lye is the mixture of ammonium salt, sodium salt and sylvite composition, and wherein, the mass ratio of ammonium salt, sodium salt and sylvite is 2:1:3.
For improving the industrial usability of the present embodiment further, between three phase separator and washing kettle, between oil water separator and preheater, de-low device and in and be equipped with intermediate storage tank between preparing tank; Photooxidation reaction device, condenser, Third monomer storage tank, perfluoroolefine storage tank, hydrolysis reactor are all connected with the freezing liquid circulatory system of control temperature; De-low device is provided with evacuation port, the condenser connecting gas-liquid separator gaseous phase outlet and perfluoroolefine storage tank is provided with offgas outlet, offgas outlet, tail gas evacuation port and evacuation port is connected with the tail gas purification tower of process tail gas.
The above is only preferred embodiment of the present invention, and not do any pro forma restriction to the present invention, every any simple modification, equivalent variations done above embodiment according to technical spirit of the present invention, all falls within protection scope of the present invention.

Claims (40)

1. one kind does not contain the fluorine-containing surfactant of perfluoro caprylic acid, it is characterized in that: described fluorine-containing surfactant is hexafluoropropylene-based and be selected from the constitutional repeating unit of an end band carboxyl that in perfluoromethoxy, Y group, oxygen perfluorovinyl sulfide, the combination of one or more forms or carboxylate by least one oxygen, and described Y group is selected from or , R=halogen or hydrogen, this fluorine-containing surfactant meets:
Acid number: <150mg/g;
Cross oxygen value: 0.001 ~ 1%;
Boiling point: 130 ~ 300 DEG C;
Surface tension: 10 ~ 30mN/m;
Critical micelle concentration: 0.05 ~ 5%;
Perfluoro caprylic acid and salt thereof: 0.
2. according to claim 1 a kind of not containing the fluorine-containing surfactant of perfluoro caprylic acid, it is characterized in that: described fluorine-containing surfactant meets following structural formula:
Or ,
Calculate by the molecular weight of polymer, the content of halogen or hydrogen: 1 ~ 15%, n:1 ~ 10, m/n:0.01 ~ 0.03.
3. according to claim 1 a kind of not containing the fluorine-containing surfactant of perfluoro caprylic acid, it is characterized in that: the molecular weight of described fluorine-containing surfactant is 200 ~ 600.
4., not containing a preparation method for the fluorine-containing surfactant of perfluoro caprylic acid, it is characterized in that: comprise the following steps:
A: perfluoroolefine, oxygen and Third monomer are at the temperature of-20 ~-25 DEG C, obtained containing acyl fluorides end group product after photooxidation;
B: will be hydrolyzed containing acyl fluorides end group product, obtains the fluorochemical oligomeric compound of an end band carboxylic acid acidic-group;
C: the fluorochemical oligomeric compound that step B is obtained is carried out, except peroxide process, obtain and be less than an end band carboxylic acid of 1g/100g and the fluorine-containing oil-based polymer of salt thereof containing peroxy-radical;
D: rear acquisition fluorine-containing surfactant finished product is neutralized to the fluorine-containing oil-based polymer that step C obtains,
This fluorine-containing surfactant finished product meets:
Acid number: <150mg/g;
Cross oxygen value: 0.001 ~ 1%;
Boiling point: 130 ~ 300 DEG C;
Surface tension: 10 ~ 30mN/m;
Critical micelle concentration: 0.05 ~ 5%;
Perfluoro caprylic acid and salt thereof: 0,
Described Third monomer is at least containing alkene or the alkynes of a non-fluorine atom.
5. kind according to claim 4 is not containing the preparation method of the fluorine-containing surfactant of perfluoro caprylic acid, it is characterized in that: in described steps A, count in mass ratio, perfluoroolefine: Third monomer=(1 ~ 10): 1.
6. kind according to claim 4 is containing the preparation method of fluorine-containing surfactant of perfluoro caprylic acid, it is characterized in that: in described steps A, photooxidation comprises: the temperature of perfluoroolefine is controlled-20 ~
-25 DEG C, the mist of oxygen and Third monomer composition is passed in perfluoroolefine, keeps ultraviolet lamp irradiation and duration of ventilation to be after 2 ~ 20h, close ultraviolet lamp, exhaust, unreacted perfluoroolefine is reclaimed after room temprature evaporation, obtained containing acyl fluorides end group product.
7. kind according to claim 6 is not containing the preparation method of the fluorine-containing surfactant of perfluoro caprylic acid, it is characterized in that: the irradiation power of described ultraviolet lamp controls at 100 ~ 1000W, selects wavelength > 300nm.
8. kind according to claim 4 is not containing the preparation method of the fluorine-containing surfactant of perfluoro caprylic acid, it is characterized in that: in described step B, hydrolytic process comprises:
B.1: by obtained to deionized water and steps A containing after the mixing of acyl fluorides end group product, stir;
B.2: the temperature that B.1 rate-determining steps prepares liquid phase fluid in material is 30 ~ 50 DEG C, continue to step B.1 prepare in material add steps A obtained containing acyl fluorides end group product, adding speed is 1 ~ 100L/H, and mixing time controls at 0.5 ~ 5h;
B.3: stir after stopping, static layering, after removing upper water, obtain the fluorochemical oligomeric compound of an end band carboxylic acid acidic-group.
9. kind according to claim 8 is not containing the preparation method of the fluorine-containing surfactant of perfluoro caprylic acid, it is characterized in that: count in mass ratio, described deionized water: what steps A was obtained contains acyl fluorides end group product=(1 ~ 5): 1.
10. kind according to claim 4 is not containing the preparation method of the fluorine-containing surfactant of perfluoro caprylic acid, it is characterized in that: in described step D, N-process comprises:
D.1: after the end band carboxylic acid that step C is obtained and the fluorine-containing oil-based polymer of salt thereof and deionized water mixing, stir;
D.2: D.1 prepare in material to step and add alkali metal hydroxide aqueous solution or ammonia aqueous solution, obtain fluorine-containing surfactant finished product.
11. 1 kinds, not containing the preparation method of the fluorine-containing surfactant of perfluoro caprylic acid, is characterized in that: described preparation method is continuous prodution process, comprises the following steps:
A: perfluoroolefine, oxygen and Third monomer continuous feed under the pressure of the temperature of 0 ~ 20 DEG C and 0.1 ~ 0.5Mpa, obtained containing acyl fluorides end group product after photooxidation;
B: after being hydrolyzed containing acyl fluorides end group product, being separated, obtain the fluorochemical oligomeric compound of an end band carboxylic acid acidic-group;
C: the fluorochemical oligomeric compound obtained in step B, after salify configuration, obtains fluorine-containing surfactant finished product,
This fluorine-containing surfactant finished product meets:
Acid number: <150mg/g;
Cross oxygen value: 0.001 ~ 0.1%;
Boiling point: 130 ~ 300 DEG C;
Surface tension: 10 ~ 30mN/m;
Critical micelle concentration: 0.05 ~ 5%;
Perfluoro caprylic acid and salt thereof: 0,
Described Third monomer is at least containing alkene or the alkynes of a non-fluorine atom.
12. is according to claim 11 a kind of not containing the preparation method of the fluorine-containing surfactant of perfluoro caprylic acid, it is characterized in that: in described steps A, the mixed material of perfluoroolefine, oxygen and Third monomer composition completes photooxidation reaction under UV-irradiation, keep the lasting charging of mixed material and the prolonged exposure of ultraviolet light, after the perfluoroolefine that gas-liquid separation is reclaimed in product, obtain containing acyl fluorides end group product.
13. is according to claim 12 a kind of not containing the preparation method of the fluorine-containing surfactant of perfluoro caprylic acid, it is characterized in that: the charging rate of described mixed material controls at 1 ~ 100L/H; Described ultraviolet lamp is UVLED lamp, and irradiation power controls at 1 ~ 100W, and selection wavelength is 300 ~ 410nm.
14. is according to claim 12 a kind of not containing the preparation method of the fluorine-containing surfactant of perfluoro caprylic acid, it is characterized in that: in described steps A, count in mass ratio, perfluoroolefine: Third monomer=(1 ~ 10): 1.
15. is according to claim 11 a kind of not containing the preparation method of the fluorine-containing surfactant of perfluoro caprylic acid, it is characterized in that: in described step B, be hydrolyzed containing adding deionized water in acyl fluorides end group product, what maintenance was hydrolyzed continues to carry out, be separated after removing gas in hydrolysate and water, obtain the fluorochemical oligomeric compound of an end band carboxylic acid acidic-group.
16. is according to claim 15 a kind of not containing the preparation method of the fluorine-containing surfactant of perfluoro caprylic acid, it is characterized in that: count in mass ratio, described deionized water: containing acyl fluorides end group product=(1 ~ 5): 1.
17. a kind of preparation methods not containing the fluorine-containing surfactant of perfluoro caprylic acid according to claim 11, it is characterized in that: in described step C, salify configuration comprises the following steps:
C.1: the fluorochemical oligomeric compound of the end band carboxylic acid acidic-group that step B obtains is washed and after water-oil separating, obtains fluorochemical polyether carboxylic acid semi-finished product;
C.2: fluorochemical polyether carboxylic acid semi-finished product are refined, fluorochemical polyether carboxylic acid finished product is obtained;
C.3: in fluorochemical polyether carboxylic acid finished product and after, obtained fluorochemical polyether surfactant finished product.
18. is according to claim 17 a kind of not containing the preparation method of the fluorine-containing surfactant of perfluoro caprylic acid, it is characterized in that: described step C.2 in, refining comprising carries out preheating and de-low process to fluorochemical polyether carboxylic acid semi-finished product, preheat temperature controls at 180 ~ 220 DEG C, and the molecular weight of de-low rear fluorochemical polyether carboxylic acid finished product controls 100 ~ 300.
19. is according to claim 17 a kind of not containing the preparation method of the fluorine-containing surfactant of perfluoro caprylic acid, it is characterized in that: described step C.3 in, neutralization is the process adding alkaline, inorganic salts and deionized water in fluorochemical polyether carboxylic acid finished product, count in mass ratio, fluorochemical polyether carboxylic acid finished product: alkaline, inorganic salts: deionized water=(20 ~ 30): (5 ~ 10): (10 ~ 30).
20. is according to claim 19 a kind of not containing the preparation method of the fluorine-containing surfactant of perfluoro caprylic acid, it is characterized in that: described alkaline, inorganic salts is the mixture of one or more compositions in ammonium salt, sodium salt, sylvite.
Prepare not containing the process system of the fluorine-containing surfactant of perfluoro caprylic acid for 21. 1 kinds, it is characterized in that: described process system comprises the photooxidation reaction device be communicated with successively, hydrolytic reaction pot, heat treatment reactor and neutralization reaction still, photooxidation reaction device is connected to perfluoroolefine storage tank and breather pipe, breather pipe is the water sealing (sealing water) pipe passing into mist in photooxidation reaction device, described mist is made up of oxygen and Third monomer, described neutralization reaction still is connected with the finished product storage tank storing fluorochemical polyether surfactant, described fluorochemical polyether surfactant meets:
Acid number: <150mg/g;
Cross oxygen value: 0.001 ~ 0.1%;
Boiling point: 130 ~ 300 DEG C;
Surface tension: 10 ~ 30mN/m;
Critical micelle concentration: 0.05 ~ 5%;
Perfluoro caprylic acid and salt thereof: 0,
Described Third monomer is at least containing alkene or the alkynes of a non-fluorine atom.
22. a kind of process systems preparing the fluorine-containing surfactant not containing perfluoro caprylic acid according to claim 21, it is characterized in that: described photooxidation reaction device is provided with the stainless steel equipment of quartzy sheath and thermocouple in being, described quartzy sheath to be evenly distributed on centered by photooxidation reaction device axis circumferentially, and be provided with two-layer from inside to outside along photooxidation reaction device axis, described photooxidation reaction device is provided with exhaust outlet.
23. a kind of process systems preparing the fluorine-containing surfactant not containing perfluoro caprylic acid according to claim 21, it is characterized in that: on described photooxidation reaction device, be provided with reflux condensing tube, perfluoroolefine from perfluoroolefine storage tank is sent in photooxidation reaction device through reflux condensing tube, and the condensation temperature of reflux condensing tube is-30 ~-60 DEG C.
24. a kind of process systems preparing the fluorine-containing surfactant not containing perfluoro caprylic acid according to claim 21, it is characterized in that: described hydrolytic reaction pot is the consersion unit of carbon steel lining fluorine or carbon steel spraying polytetrafluoro coating, hydrolytic reaction pot is provided with the liquid phase charge door, evacuation port and the cooling jacket that add for photooxidation reaction product and deionized water, in hydrolytic reaction pot, is provided with agitator.
25. a kind of process systems preparing the fluorine-containing surfactant not containing perfluoro caprylic acid according to claim 21, it is characterized in that: described heat treatment reactor is the consersion unit of carbon steel lining fluorine or carbon steel polytetrafluoroethylene spray, described heat treatment reactor is provided with agitator, heating inner coil pipe, heating jacket, conduction oil device.
26. a kind of process systems preparing the fluorine-containing surfactant not containing perfluoro caprylic acid according to claim 21, it is characterized in that: described neutralization reaction still is stainless steel cauldron, neutralization reaction still is provided with the charge door and cooling water jecket that add for alkaline solution and deionized water, in neutralization reaction still, is provided with agitator.
Prepare not containing the continuous process system of the fluorine-containing surfactant of perfluoro caprylic acid for 27. 1 kinds, it is characterized in that: described process system comprises the photooxidation reaction loop be connected successively, hydrolysis unit and salify dispensing unit, photooxidation reaction loop comprises perfluoroolefine storage tank, Third monomer storage tank, photooxidation reaction device and gas-liquid separator, air and liquid mixer is connected with at the entrance of photooxidation reaction device, perfluoroolefine, Third monomer and oxygen send into photooxidation reaction device through air and liquid mixer, gas-liquid separator is connected in the outlet of photooxidation reaction device, the gaseous phase outlet of gas-liquid separator is connected with perfluoroolefine storage tank, the liquid-phase outlet of gas-liquid separator is connected with hydrolysis unit, salify dispensing unit is connected with the finished product storage tank storing fluorochemical polyether surfactant, and described fluorochemical polyether surfactant meets:
Acid number: <150mg/g;
Cross oxygen value: 0.001 ~ 0.1%;
Boiling point: 130 ~ 300 DEG C;
Surface tension: 10 ~ 30mN/m;
Critical micelle concentration: 0.05 ~ 5%,
Perfluoro caprylic acid and salt thereof: 0,
Described Third monomer is at least containing alkene or the alkynes of a non-fluorine atom.
28. a kind of continuous process systems preparing the fluorine-containing surfactant not containing perfluoro caprylic acid according to claim 27, it is characterized in that: described photooxidation reaction loop also comprises the condenser of precooling reaction raw materials and precooling gas-liquid separator gas recovery, the quantity of described condenser is three groups, and one group is connected on Third monomer storage tank; One group is connected on perfluoroolefine storage tank; One group is connected between perfluoroolefine storage tank and the gaseous phase outlet of gas-liquid separator.
29. a kind of continuous process systems preparing the fluorine-containing surfactant not containing perfluoro caprylic acid according to claim 27, it is characterized in that: described photooxidation reaction device is the tubular reactor be composed in series by glass tube, series connection direction along glass tube is evenly arranged the ultraviolet aperture of more than a group, often organize ultraviolet aperture to be made up of the LED uviol lamp pearl be circumferentially evenly arranged apart from glass tube external diameter 1 ~ 5mm, the light-emitting area of LED uviol lamp pearl is corresponding on glass tube.
30. a kind of continuous process systems preparing the fluorine-containing surfactant not containing perfluoro caprylic acid according to claim 29, it is characterized in that: the quantity of described glass tube is 50 ~ 100, the length of every root glass tube is 1 ~ 2m.
31. a kind of continuous process systems preparing the fluorine-containing surfactant not containing perfluoro caprylic acid according to claim 29, it is characterized in that: the quantity of described LED uviol lamp pearl is 50 ~ 100, the wavelength of each LED uviol lamp pearl is 365 ~ 405nm.
32. a kind of continuous process systems preparing the fluorine-containing surfactant not containing perfluoro caprylic acid according to claim 28, it is characterized in that: described hydrolysis unit comprises circulation, the hydrolysis reactor be connected with the liquid-phase outlet of gas-liquid separator, connect the three phase separator of hydrolysis reactor outlet, the entrance of hydrolysis reactor is all connected with circulation with the aqueous phase outlet of three phase separator, tail gas evacuation port is provided with at the gaseous phase outlet of three phase separator, the oil phase outlet of three phase separator is provided with the fluorochemical oligomeric compound storage tank be connected with salify dispensing unit.
33. a kind of continuous process systems preparing the fluorine-containing surfactant not containing perfluoro caprylic acid according to claim 32, is characterized in that: in described hydrolysis reactor, be provided with mixing baffle.
34. a kind of continuous process systems preparing the fluorine-containing surfactant not containing perfluoro caprylic acid according to claim 32, it is characterized in that: described hydrolysis reactor is the tubular reactor be composed in series by steel lining resin pipeline, the internal diameter of steel lining resin pipeline is 20 ~ 40mm.
35. a kind of continuous process systems preparing the fluorine-containing surfactant not containing perfluoro caprylic acid according to claim 32, it is characterized in that: described salify dispensing unit comprise successively be connected washing process, rectification flow and in and flow process, washing process comprises the washing kettle be connected with fluorochemical oligomeric compound storage tank successively, first oil water separator and the second oil water separator, washing kettle entrance, first oil water separator aqueous phase outlet, second oil water separator aqueous phase outlet is all connected with circulation, second oil water separator oil phase outlet is provided with the fluorochemical polyether carboxylic acid semi-finished product storage tank be connected with rectification flow, during finished product storage tank is connected to and in flow process.
36. a kind of continuous process systems preparing the fluorine-containing surfactant not containing perfluoro caprylic acid according to claim 35, it is characterized in that: described rectification flow comprises the preheater that is connected with fluorochemical polyether carboxylic acid semi-finished product storage tank successively and de-low device, described de-low device is provided with in the fluorochemical polyether carboxylic acid finished product storage tank that is connected with flow process and evacuation port.
37. a kind of continuous process systems preparing the fluorine-containing surfactant not containing perfluoro caprylic acid according to claim 36, it is characterized in that: in described and flow process comprise in and batch tank, in and batch tank entrance be connected with alkali lye batch tank and pure water batch tank, in and batch tank export be connected finished product batch tank.
38. a kind of continuous process systems preparing the fluorine-containing surfactant not containing perfluoro caprylic acid according to claim 36, is characterized in that: on described preheater and de-low device, be all connected with the heat-conducting oil system providing thermal source.
39. a kind of according to any one of claim 32 ~ 38 prepare not containing the continuous process system of the fluorine-containing surfactant of perfluoro caprylic acid, it is characterized in that: the freezing liquid circulatory system being all connected with control temperature on described photooxidation reaction device, condenser, Third monomer storage tank, perfluoroolefine storage tank, hydrolysis reactor.
40. a kind of according to any one of claim 36 ~ 38 prepare not containing the continuous process system of the fluorine-containing surfactant of perfluoro caprylic acid, it is characterized in that: on the condenser connecting gas-liquid separator gaseous phase outlet and perfluoroolefine storage tank, be provided with offgas outlet, described offgas outlet, tail gas evacuation port and evacuation port be connected with the tail gas purification tower of process tail gas.
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CN112675780A (en) * 2020-12-25 2021-04-20 天津长芦新材料研究院有限公司 Fluorine-containing surfactant, preparation method and application
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