CN105148794A - Production technology for preparing fluorine-containing surfactant free from perfluoro caprylic acid - Google Patents
Production technology for preparing fluorine-containing surfactant free from perfluoro caprylic acid Download PDFInfo
- Publication number
- CN105148794A CN105148794A CN201510635339.3A CN201510635339A CN105148794A CN 105148794 A CN105148794 A CN 105148794A CN 201510635339 A CN201510635339 A CN 201510635339A CN 105148794 A CN105148794 A CN 105148794A
- Authority
- CN
- China
- Prior art keywords
- fluorine
- caprylic acid
- containing surfactant
- perfluoro caprylic
- surfactant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a production technology for preparing a fluorine-containing surfactant free from perfluoro caprylic acid. The production technology includes the steps of photooxidation, hydrolysis, peroxide removing treatment and neutralization, perfluoroolefine, oxygen and a third monomer serve as reaction raw materials and are prepared into a fluorine-containing surfactant finished product with a C-O-C ether bond structure as the structural body, the finished product index meets the requirement that the surfactant is free from perfluoro caprylic acid and salts thereof, the surfactant is easy to decompose in the nature, the finished product index meets the data range that the peroxide value is 0.001-1%, and the surface tension is 10-30 mN/m; the fluorine-containing surfactant is of an amphiphilic structure of surfactants and suitable for industrial mass production.
Description
Technical field
The present invention is a kind of preparation not containing the production technology of the fluorine-containing surfactant of perfluoro caprylic acid, is specifically related to the synthesis route being used as the fluoropolymer that surfactant uses, 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 production technology preparing the fluorine-containing surfactant not containing perfluoro caprylic acid, with perfluoroolefine, oxygen and Third monomer are as reaction raw materials, successively through photooxidation, hydrolysis, except peroxide process and neutralization four steps fluorine-containing surfactant finished product that to obtain with C-O-C diether linkage structure be main structure body, finished product index not only meets not containing perfluoro caprylic acid and salt thereof, easily be decomposed in the Nature, containing meeting oxygen value 0.001 ~ 1%, the data area of surface tension 10 ~ 30mN/m, there is the amphiphilic structure of surfactant, Suitable commercial large-scale production.
The present invention is achieved through the following technical solutions: a kind of production technology preparing the fluorine-containing surfactant not containing perfluoro caprylic acid, is characterized in that: comprise the following steps:
A: at the temperature of-20 ~-25 DEG C, sends perfluoroolefine, oxygen and Third monomer into photooxidation reaction device, obtained containing acyl fluorides end group product after photooxidation;
B: hydrolytic reaction pot will be sent into containing acyl fluorides end group product, the fluorochemical oligomeric compound of an obtained end band carboxylic acid acidic-group after hydrolysis;
C: fluorochemical oligomeric compound obtained for step B is sent into heat treatment reactor, is less than an end band carboxylic acid of 1g/100g and the fluorine-containing oil-based polymer of salt thereof through obtaining after peroxide process containing peroxy-radical;
D: send into neutralization reaction still to the fluorine-containing oil-based polymer that step C obtains, obtain fluorine-containing surfactant finished product after neutralization, this fluorine-containing surfactant finished product sends into finished product storage tank.
Described 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.
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, crossing oxygen value can control in the scope of 0.001 ~ 1%, preferably can control in the scope of 0.001 ~ 0.1%, eliminate the production safety hidden danger of downstream manufacturers, possesses good commercial application prospect.
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 ~ 600, it is crossed oxygen value and meets 0.001 ~ 1%.
Described steps A comprises: at the temperature of-20 ~-25 DEG C, perfluoroolefine is added in photooxidation reaction device, the mist of oxygen and Third monomer composition is passed in photooxidation reaction device, 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.
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.
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, described step B comprises:
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 ~ 50 DEG C, continue to add in hydrolytic reaction pot 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.
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 containing acyl fluorides end group product and deionized water obtained for steps A, 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, in control still, temperature of charge is not higher than 300 DEG C, 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 at 1 ~ 0.8g/100g.
Described step D comprises:
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 or ammonia aqueous solution, obtain fluorine-containing surfactant finished product.
The reaction equation of N-process is as follows:
described neutralization reaction still is stainless steel cauldron, neutralization reaction still is provided with the charge door and cooling water jecket that provide alkaline solution and deionized water to add, 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.
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) 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.
(6) fluorine-containing surfactant that the present invention relates to can adopt batch production technique to be prepared, for obtaining the fluorine-containing surfactant finished product that oxygen value meets 0.001 ~ 1%, adopt the rational proportion of perfluoroolefine, oxygen and Third monomer, and reasonable temperature and normal pressure control, realize the control of crossing oxygen value content in product, prove through practical operation, said method can obtain the fluorine-containing surfactant finished product not containing perfluoro caprylic acid and salt thereof that oxygen value meets 0.001 ~ 1%, has good market value.
(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.
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 preparation not containing the production technology of the fluorine-containing surfactant of perfluoro caprylic acid, comprises the following steps:
A: at the temperature of-20 DEG C, sends perfluoroolefine, oxygen and Third monomer into photooxidation reaction device, obtained containing acyl fluorides end group product after photooxidation;
B: hydrolytic reaction pot will be sent into containing acyl fluorides end group product, the fluorochemical oligomeric compound of an obtained end band carboxylic acid acidic-group after hydrolysis;
C: fluorochemical oligomeric compound obtained for step B is sent into heat treatment reactor, is less than an end band carboxylic acid of 1g/100g and the fluorine-containing oil-based polymer of salt thereof through obtaining after peroxide process containing peroxy-radical;
D: send into neutralization reaction still to the fluorine-containing oil-based polymer that step C obtains, obtain fluorine-containing surfactant finished product after neutralization, this fluorine-containing surfactant finished product sends into finished product storage tank.
The fluorine-containing surfactant finished product that the present embodiment relates to 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,
Above-mentioned Third monomer is at least containing alkene or the alkynes of a non-fluorine atom, as chloroacetylene.
Embodiment 2:
The preparation that the present embodiment relates to does not comprise the following steps containing the production technology of the fluorine-containing surfactant of perfluoro caprylic acid:
A: at the temperature of-25 DEG C, sends perfluoroolefine, oxygen and Third monomer into photooxidation reaction device, obtained containing acyl fluorides end group product after photooxidation;
B: hydrolytic reaction pot will be sent into containing acyl fluorides end group product, the fluorochemical oligomeric compound of an obtained end band carboxylic acid acidic-group after hydrolysis;
C: fluorochemical oligomeric compound obtained for step B is sent into heat treatment reactor, is less than an end band carboxylic acid of 1g/100g and the fluorine-containing oil-based polymer of salt thereof through obtaining after peroxide process containing peroxy-radical;
D: send into neutralization reaction still to the fluorine-containing oil-based polymer that step C obtains, obtain fluorine-containing surfactant finished product after neutralization, this fluorine-containing surfactant finished product sends into finished product storage tank.
The fluorine-containing surfactant finished product that the present embodiment relates to 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,
Above-mentioned Third monomer is at least containing alkene or the alkynes of a non-fluorine atom, as vinylidene.
Embodiment 3:
The difference of the present embodiment and embodiment 1 is: in the steps A that the present embodiment relates to, and the mass ratio of perfluoroolefine and Third monomer is 1:1.
Embodiment 4:
The difference of the present embodiment and embodiment 2 is: in the steps A that the present embodiment relates to, and the mass ratio of perfluoroolefine and Third monomer is 10:1.
Embodiment 5:
The difference of the present embodiment and embodiment 1 is: the steps A related at the present embodiment comprises: at the temperature of-25 DEG C, perfluoroolefine is added in photooxidation reaction device, the mist of oxygen and Third monomer composition 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 the present embodiment, the irradiation power of ultraviolet lamp controls at 100W, and selection wavelength is 305nm.
Embodiment 6:
The difference of the present embodiment and embodiment 2 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.Photooxidation reaction device is provided with reflux condensing tube, and the perfluoroolefine from perfluoroolefine storage tank is sent in photooxidation reaction device through reflux condensing tube, and the condensation temperature of reflux condensing tube controls at-30 DEG C.
Embodiment 7:
The difference of the present embodiment and embodiment 1 is: the step B related at the present embodiment comprises:
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 1:1.
Embodiment 8:
The difference of the present embodiment and embodiment 2 is: the step B related at the present embodiment comprises:
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 5:1.
Embodiment 9:
The difference of the present embodiment and embodiment 7 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 containing acyl fluorides end group product and deionized water that obtain for steps A, in hydrolytic reaction pot, is provided with agitator.
Embodiment 10:
The difference of the present embodiment and embodiment 1 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 11:
The difference of the present embodiment and embodiment 2 is: the step D that the present embodiment relates to comprises:
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.
Embodiment 12:
The difference of the present embodiment and embodiment 11 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 13:
The preparation technology not containing the fluorine-containing surfactant of perfluoro caprylic acid that the present embodiment relates to 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 vinyl chloride) form is passed in photooxidation reaction device, 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.In above process, perfluoroolefine, the mass ratio of oxygen and Third monomer is 1:100:1, 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 1000W, selection wavelength is 480nm.
(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 35 DEG C, continue to add in hydrolytic reaction pot steps A obtained containing acyl fluorides end group product, adding speed is 80L/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 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 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 14:
The preparation technology not containing the fluorine-containing surfactant of perfluoro caprylic acid that the present embodiment relates to 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 12h, 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 100:50:1, 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-50 DEG C, UV-irradiation power in quartz sheath controls at 700W, selection wavelength is 385nm.
(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 60L/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 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 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 15:
The preparation technology not containing the fluorine-containing surfactant of perfluoro caprylic acid that the present embodiment relates to is as follows:
(A) at the temperature of-24 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 15h, 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 80:1:1, 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-55 DEG C, UV-irradiation power in quartz sheath controls at 500W, selection wavelength is 440nm.
(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 45 DEG C, continue to add in hydrolytic reaction pot steps A obtained containing acyl fluorides end group product, adding speed is 60L/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 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 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.
The index parameter of the fluorine-containing surfactant prepared by above-described embodiment 1 ~ 15 carries out detecting (detection method is undertaken by national standard) and data statistics, as shown in table 1.
Table 1
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 (12)
1. prepare not containing a production technology for the fluorine-containing surfactant of perfluoro caprylic acid, it is characterized in that: comprise the following steps:
A: at the temperature of-20 ~-25 DEG C, sends perfluoroolefine, oxygen and Third monomer into photooxidation reaction device, obtained containing acyl fluorides end group product after photooxidation;
B: hydrolytic reaction pot will be sent into containing acyl fluorides end group product, the fluorochemical oligomeric compound of an obtained end band carboxylic acid acidic-group after hydrolysis;
C: fluorochemical oligomeric compound obtained for step B is sent into heat treatment reactor, is less than an end band carboxylic acid of 1g/100g and the fluorine-containing oil-based polymer of salt thereof through obtaining after peroxide process containing peroxy-radical;
D: send into neutralization reaction still to the fluorine-containing oil-based polymer that step C obtains, obtain fluorine-containing surfactant finished product after neutralization, this fluorine-containing surfactant finished product sends into finished product storage tank,
Described 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.
2. a kind of production technology preparing the fluorine-containing surfactant not containing perfluoro caprylic acid according to claim 1, is characterized in that: in described steps A, count in mass ratio, perfluoroolefine: Third monomer=(1 ~ 10): 1.
3. a kind of production technology preparing the fluorine-containing surfactant not containing perfluoro caprylic acid according to claim 1, it is characterized in that: described steps A comprises: at the temperature of-20 ~-25 DEG C, perfluoroolefine is added in photooxidation reaction device, the mist of oxygen and Third monomer composition is passed in photooxidation reaction device, 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.
4. a kind of production technology preparing the fluorine-containing surfactant not containing perfluoro caprylic acid according to claim 3, is characterized in that: the irradiation power of described ultraviolet lamp controls at 100 ~ 1000W, selects wavelength > 300nm.
5. a kind of production technology preparing the fluorine-containing surfactant not containing perfluoro caprylic acid according to claim 1, 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.
6. a kind of production technology preparing the fluorine-containing surfactant not containing perfluoro caprylic acid according to claim 5, 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.
7. a kind of production technology preparing the fluorine-containing surfactant not containing perfluoro caprylic acid according to claim 1, is characterized in that: described step B comprises:
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 ~ 50 DEG C, continue to add in hydrolytic reaction pot 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.
8. a kind of production technology preparing the fluorine-containing surfactant not containing perfluoro caprylic acid according to claim 7, 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.
9. a kind of production technology preparing the fluorine-containing surfactant not containing perfluoro caprylic acid according to claim 7, 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 containing acyl fluorides end group product and deionized water that obtain for steps A, in hydrolytic reaction pot, is provided with agitator.
10. a kind of production technology preparing the fluorine-containing surfactant not containing perfluoro caprylic acid according to claim 1, 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.
11. a kind of production technologies preparing the fluorine-containing surfactant not containing perfluoro caprylic acid according to claim 1, is characterized in that: described step D comprises:
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 or ammonia aqueous solution, obtain fluorine-containing surfactant finished product.
12. a kind of production technologies preparing the fluorine-containing surfactant not containing perfluoro caprylic acid according to claim 11, 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510635339.3A CN105148794A (en) | 2015-09-30 | 2015-09-30 | Production technology for preparing fluorine-containing surfactant free from perfluoro caprylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510635339.3A CN105148794A (en) | 2015-09-30 | 2015-09-30 | Production technology for preparing fluorine-containing surfactant free from perfluoro caprylic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105148794A true CN105148794A (en) | 2015-12-16 |
Family
ID=54790019
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510635339.3A Withdrawn CN105148794A (en) | 2015-09-30 | 2015-09-30 | Production technology for preparing fluorine-containing surfactant free from perfluoro caprylic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105148794A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105170018A (en) * | 2015-09-30 | 2015-12-23 | 成都晨光博达橡塑有限公司 | Fluorosurfactant free of perfluorooctanoic acid as well as preparation method and process system of fluorosurfactant |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5051158A (en) * | 1988-05-02 | 1991-09-24 | Ausimont S.R.L. | Process for preparing controlled molecular weight perfluoropolyethers having perfluoroalkyl or perfluorochloroalkyl end groups |
| US5143589A (en) * | 1988-05-02 | 1992-09-01 | Ausimont S.R.L. | Perfluoropolyethers containing a halogen different from fluorine and having an acid end group |
| CN103073410A (en) * | 2012-12-30 | 2013-05-01 | 江苏梅兰化工有限公司 | Preparation method of fluoro-ether carboxylic acid surfactant |
| CN103936905A (en) * | 2014-05-09 | 2014-07-23 | 成都晨光博达橡塑有限公司 | Fluorine-containing polymer and preparation method thereof |
| CN103951772A (en) * | 2014-05-09 | 2014-07-30 | 成都晨光博达橡塑有限公司 | Method suitable for preparing fluorine-containing polymer free from perfluoro caprylic acid or perfluorooctane sulfonic acid |
| CN105170018A (en) * | 2015-09-30 | 2015-12-23 | 成都晨光博达橡塑有限公司 | Fluorosurfactant free of perfluorooctanoic acid as well as preparation method and process system of fluorosurfactant |
-
2015
- 2015-09-30 CN CN201510635339.3A patent/CN105148794A/en not_active Withdrawn
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5051158A (en) * | 1988-05-02 | 1991-09-24 | Ausimont S.R.L. | Process for preparing controlled molecular weight perfluoropolyethers having perfluoroalkyl or perfluorochloroalkyl end groups |
| US5143589A (en) * | 1988-05-02 | 1992-09-01 | Ausimont S.R.L. | Perfluoropolyethers containing a halogen different from fluorine and having an acid end group |
| CN103073410A (en) * | 2012-12-30 | 2013-05-01 | 江苏梅兰化工有限公司 | Preparation method of fluoro-ether carboxylic acid surfactant |
| CN103936905A (en) * | 2014-05-09 | 2014-07-23 | 成都晨光博达橡塑有限公司 | Fluorine-containing polymer and preparation method thereof |
| CN103951772A (en) * | 2014-05-09 | 2014-07-30 | 成都晨光博达橡塑有限公司 | Method suitable for preparing fluorine-containing polymer free from perfluoro caprylic acid or perfluorooctane sulfonic acid |
| CN105170018A (en) * | 2015-09-30 | 2015-12-23 | 成都晨光博达橡塑有限公司 | Fluorosurfactant free of perfluorooctanoic acid as well as preparation method and process system of fluorosurfactant |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105170018A (en) * | 2015-09-30 | 2015-12-23 | 成都晨光博达橡塑有限公司 | Fluorosurfactant free of perfluorooctanoic acid as well as preparation method and process system of fluorosurfactant |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105170018A (en) | Fluorosurfactant free of perfluorooctanoic acid as well as preparation method and process system of fluorosurfactant | |
| CN102974268B (en) | Alkylbenzyl polyoxyethylene ether betaine surfactant and its preparation method and use | |
| CN106316809B (en) | A method of preparing perfluorethyl isopropyl ketone | |
| CN102432961B (en) | Composite heat stabilizer for polyvinyl chloride (PVC), and preparation method for composite heat stabilizer | |
| CN102151515A (en) | Amino acid type fluorocarbon surfactant, synthesis method and application | |
| CN103936905B (en) | A kind of fluoropolymer and preparation method thereof | |
| EP2781500A1 (en) | Method for preparing fluorine-containing vinyl ether | |
| CN104119544A (en) | Preparing method of tetrafluoroethylene-hexafluoropropylene copolymer concentrated dispersion liquid | |
| CN104945549B (en) | Ethene chlorotrifluoroethylene, its preparation method and application with stable end groups structure | |
| CN105254476A (en) | Method for preparing fluorine-containing halogenated ether | |
| CN104725283A (en) | Trifluoromethanesulfonic acid preparation method | |
| CN105111353A (en) | Preparation method for special low-temperature-resistant fluororubber | |
| CN105148794A (en) | Production technology for preparing fluorine-containing surfactant free from perfluoro caprylic acid | |
| CN105924561A (en) | Preparation method of modified teflon resin | |
| CN106893022B (en) | A kind of aqueous broken emulsion of polymer containing fluorin and preparation method thereof | |
| CN101302262B (en) | Preparation of ethylene-tetrafluoroethylene copolymer | |
| CN105344289A (en) | Fluorine-containing surfactant free of perfluorooctanoic acid and salts thereof | |
| CN103193904A (en) | Method for preparing fluorine-containing polymer through dispersion method | |
| CN105170017A (en) | Fluorosurfactant free of perfluorooctanoic acid | |
| CN105111352A (en) | Preparation method for special fluoroether oligomer | |
| CN106893090B (en) | A kind of preparation method and products therefrom of perfluoro polyether oil | |
| CN101455908B (en) | High pure hexafluoropropylene oxide preparation method using extraction rectification | |
| CN105330520B (en) | A kind of method for synthesizing double (2,3 dibromopropyl) ethers of tetrabromobisphenol A in water phase | |
| CN100376553C (en) | Full halothane sulfonic acid salts, preparation method and application | |
| CN105344288A (en) | Continuous production technology of fluorine-containing surfactant without perfluorocaprylic acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C04 | Withdrawal of patent application after publication (patent law 2001) | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20151216 |