CN101745339A - Succinic acid fluorine-containing alcohol ester sulfonate surfactant and preparation method thereof - Google Patents
Succinic acid fluorine-containing alcohol ester sulfonate surfactant and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a succinic acid fluorine-containing alcohol ester sulfonate surfactant, which has the structural formula as follows: wherein n is an integer between 4 and 8, and m is an integer between 0 and 2. The invention also discloses a preparation method of succinic acid fluorine-containing alcohol ester sulfonate surfactant. The surfactant can reduce the surface tension of the liquid and can improve the wettability of the coating mixture on a matrix by adding to the coating mixture, also can be discharged out with the metabolism of the human body, reduces the harm to the human body, can be used in the fields like dispersion polymerization synthesized by fluorine polymer, spinning, papermaking, coating and cosmetics and is a good substitute for PFOS and PFOA.
Description
Technical field
The present invention relates to a kind of succinic acid fluorine-containing alcohol ester sulfonate surfactant and preparation method thereof.
Background technology
Fluorine-containing surfactant has high surface, high heat-resistant stability, high chemical stability and not only hydrophobic but also hate the wet goods good characteristic, can be used for numerous industrial circles such as chemistry, fluorine chemical, biology, medicine, machinery, weaving, electric, papermaking, pigment, coating, printing ink, glass ceramics, metallurgy, fuel, leather, photosensitive material, building, oil and fire-fighting.At present, the fluorine-containing surfactant of extensive use is perfluoro octyl sulfonic acid compound (PFOS) and full sad compound (PFOA), PFOS is widely used in fields such as weaving, leather, semiconductor manufacturing, papermaking, coating, fire-fighting and cosmetics, and PFOA is mainly used in the synthetic of the dispersion fluororesin of fluorine chemical and fluorubber etc.
European Parliament has issued " about the instruction of sale of restriction perfluoro octyl sulfonic acid and use " (2006/122/EC) on December 27th, 2006, and reaffirm the regulation that relevant PFOS that European Parliament passed through on October 25th, 2006 limits the quantity of, and will before 27 days December in 2007, become the state's laws of each member state, played enforcement on June 27th, 2008.In the instruction, PFOS limit the quantity of for: (1) its mass fraction met or exceeded 0.005% o'clock, can not be used as raw materials for production and formulation components; (2) limiting the quantity of of semi-products is 0.1%; (3) to limit the quantity of be 10 μ g/m for textile and coating material
2Simultaneously, instruction proposes fluorine-containing sad (Perfluorooctanic Acid, abbreviation PFOA, molecular formula C
7F
15COOH) and salt suspect similar risk to be arranged to PFOS.Report that PFOS and 96 kinds of materials relevant with PFOS are all in the forbidding scope.The forbidding of PFOS will have very big harmful effect to the production and the product quality in fields such as weaving, leather, semiconductor manufacturing, papermaking, coating, fire-fighting and cosmetics.
The persistence of perfluoro octyl sulfonic acid compound (PFOS) and perfluoro caprylic acid compound (PFOA) is extremely strong, is the organic pollution of difficult decomposition, and extremely strong transfer ability is arranged, and experimental study shows that PFOS and PFOA can build up in the organic-biological body.PFOS in the water shifts to comprising that a human high position is biological by long-pending effect of hydrobiological richness and food chain, toxic side effect, zoopery shows, PFOS and PFOA can cause toxicity such as liver, reproduction, growth, heredity and immunity, PFOS has carcinogenesis, and the relevant report of SAB of American National Environmental Protection Agency is described as PFOA " possible (likely) carcinogenic substance.Therefore, the synthesizing new fluorine-containing surfactant, the substitute of seeking PFOS and PFOA is the problem of World Focusing.
The difficult biological decomposition of PFOS and PFOA, the easy character of building up in vivo are by its structures shape, because the carbon-fluorine bond bond energy height in its structure causes all difficulty destruction of carbon-fluorine bond and fluorocarbon chain, are difficult for degraded, carbon fluorine chain (C
8: F (CF
2)-) hydrophobic oleophobic is easily built up it in vivo, is difficult for discharging.Existing discover shorten fluorine-containing surfactant-CF
2-carbon chain lengths its metabolism along with human body is excreted, thereby improve fluorine-containing surfactant in the human body deposition conditions, having the existing good surface-active of fluorine-containing surfactant, the stability of the hydrophobic alkyl of part fluoro, is not again the organic matter of difficult degradation.
Summary of the invention
The present invention provides a kind of fluorine-containing surfactant---succinic acid fluorine-containing alcohol ester sulfonate surfactant for fear of PFOS and the structural shortcoming of PFOA.This surfactant can effectively reduce surface tension of liquid, increases wetability, and can excrete along with the metabolism of human body, reduces the injury to human body, is the good substitute of PFOS and PFOA.
Another object of the present invention provides the preparation method of this surfactant.
The present invention realizes by following measure:
The present invention is a raw material with fluorine hydrogen carbon alcohol or the ether with ω-H and α-H, has obtained a kind of fluorine-containing surfactant---succinic acid fluorine-containing alcohol ester sulfonate surfactant.What the fluorine hydrogen carbon alcohol of described ω-H and α-H or ether were represented is hydrogeneous fluorine hydrogen carbon alcohol of head end and tail end or fluorine hydrogen carbon ether, and ω-H represents head end hydrogen, and what α-H represented is tail end hydrogen, the H (CF that the present invention uses
2) nCH
2OH and H (CF
2) nCH
2O (CH
2CH
2O) m H can both buy in market, all has ω-H and α-H.
Succinic acid fluorine-containing alcohol ester sulfonate surfactant of the present invention has following structural:
Wherein, n is the integer of 4-8, and m is the integer of 0-2.
The preferred version of this surfactant is: n=8, m=0,1,2.
The preferred version of this surfactant is: n=6, m=0,1,2;
The preferred version of this surfactant is: n=4, m=0,1,2.
A kind of preparation method of succinic acid fluorine-containing alcohol ester sulfonate surfactant may further comprise the steps:
(1) under the situation of catalyst and azeotropic agent existence, with H (CF
2) nCH
2OH and maleic anhydride add thermal agitation under nitrogen protection, reaction finishes the back and obtains succinic acid fluorine-containing alcohol ester A by distilling and washing to remove for unreacted pure and mild maleic anhydride, and structural formula is
(2) above-mentioned succinic acid fluorine-containing alcohol ester A is joined in the reactor, drip mass concentration then and be 20～40% aqueous solution of sodium bisulfite, reaction at a certain temperature, reaction finishes afterreaction liquid layering or precipitation occurs, obtains succinic acid fluorine-containing alcohol ester sulfonate surfactant through separatory or filtration.
H (CF in the described step (1)
2) nCH
2The mol ratio of OH and maleic anhydride is 2～4: 1, and described catalyst is a p-methyl benzenesulfonic acid, and consumption is 3-8g, and reaction temperature is 80-140 ℃, and the reaction time is 6-18h.Azeotropic agent effect in the reaction is to remove the water that is generated in the dereaction, prevent to react and carry out round about, it is prior art well known by persons skilled in the art, its consumption has no special requirements, reaction is got final product by correct direction, according to the difference of reaction vessel, be generally 1/3rd to 1/4th of reaction vessel volume.
The mol ratio 1: 1.07～3.3 of amber fluorine-containing alcohol ester A of acid and sodium hydrogensulfite in the described step (2), reaction temperature is 92～145 ℃, the solution of sodium bisulfite dropping time is 1.5～2 hours, dropwises afterreaction 6～18h.Considering that temperature raises has water evaporates influence reaction and carries out, in course of reaction or initial reaction stage can add a certain amount of water.
A kind of preparation method of succinic acid fluorine-containing alcohol ester sulfonate surfactant may further comprise the steps:
(1) under the situation of catalyst and azeotropic agent existence, with H (CF
2) nCH
2O (CH
2CH
2O) mH and maleic anhydride add thermal agitation in nitrogen protection, and reaction finishes the back will remove for unreacted ether and maleic anhydride by distillation and washing and obtain succinic acid fluorine-containing alcohol ester B, and structural formula is
(2) above-mentioned succinic acid fluorine-containing alcohol ester B is joined in the reactor, drip mass concentration then and be 20～40% aqueous solution of sodium bisulfite, reaction at a certain temperature, reaction finishes afterreaction liquid layering or precipitation occurs, obtains succinic acid fluorine-containing alcohol ester sulfonate surfactant through separatory or filtration.
Maleic anhydride and H (CF in the step (1)
2) nCH
2O (CH
2CH
2O) mol ratio of m H is 1: 2～4, and described catalyst is a p-methyl benzenesulfonic acid, and consumption is 3-8g, and reaction temperature is 80-140 ℃, and the reaction time is 6-18h.Azeotropic agent effect in the reaction is to remove the water that is generated in the dereaction, prevent to react and carry out round about, it is prior art well known by persons skilled in the art, its consumption has no special requirements, reaction is got final product by correct direction, according to the difference of reaction vessel, be generally 1/3rd to 1/4th of reaction vessel volume.
The mol ratio 1: 1.07～3.3 of succinic acid fluorine-containing alcohol ester B and sodium hydrogensulfite in the step (2), reaction temperature is 92～145 ℃, the solution of sodium bisulfite dropping time is 1.5～2 hours, dropwises afterreaction 6～18h.Considering that temperature raises has water evaporates influence reaction and carries out, in course of reaction or initial reaction stage can add a certain amount of water.
Beneficial effect of the present invention is as follows:
Surfactant of the present invention can reduce surface tension of liquid, it is added to can improve the wetability of coating compound on matrix in the coating compound.
This fluorine-containing surfactant can be able to excrete along with the metabolism of human body, reduces the injury to human body, can be used for the synthetic fields such as dispersin polymerization, weaving, papermaking, coating and cosmetics of fluoropolymer polymer, is the good substitute of PFOS and PFOA.
Preparation method of the present invention is simple to operate, and mild condition is easy to industrialized production.
The specific embodiment
Below by specific embodiment the present invention is further elaborated.
Embodiment 1
(1) in being equipped with the four-hole round bottom 500ml flask of agitator, heating jacket, condenser, nitrogen inlet, water knockout drum and thermometer, adds 376g H (CF
2)
6CH
2OCH
2CH
2OH, 50g maleic anhydride, 6g p-methyl benzenesulfonic acid and 150ml azeotropic agent toluene.Agitating heating refluxes under nitrogen protection, and keeping temperature is 80 ℃ of reactions 18 hours, can judge the progress of reaction according to the amount of the water that produces in the water knockout drum, and reaction finishes the back will be unreacted H (CF by distillation and washing
2)
6CH
2OCH
2CH
2OH and maleic anhydride are removed and are obtained succinic acid fluorine-containing alcohol ester B, and structural formula is:
(2) the 20.81g sodium hydrogensulfite being made into mass concentration is 20% the aqueous solution, stirs, and solution is faint yellow, is positioned over to prepare in the normal pressure balance dropping funel to drip.
Toward the flat synthetic succinic acid fluorine-containing alcohol ester B of 160g previous step that adds of four-hole, add the redistilled water of 10g, begin to add thermal agitation, when temperature is 95 ℃, begin to drip the solution of sodium bisulfite for preparing, dripped 1.5 hours, and dropwised the back and keep this temperature to react again 18 hours.Reaction finishes the layering of afterreaction liquid, obtains product through separatory, and wash products so that wash unreacted ester off, obtains fluorine-containing surfactant repeatedly.
Embodiment 2
(1) in being equipped with the four-hole round bottom 500ml flask of agitator, heating jacket, condenser, nitrogen inlet, water knockout drum and thermometer, adds 464g H (CF
2)
4CH
2OH, 50g maleic anhydride, 8g p-methyl benzenesulfonic acid add 130ml azeotropic agent cyclohexane again.Agitating heating refluxes under nitrogen protection, and keeping temperature is 140 ℃ of reactions 7 hours, can judge the progress of reaction according to the amount of the water that produces in the water knockout drum, and reaction finishes the back will be unreacted H (CF by distillation and washing
2)
4CH
2OH and maleic anhydride are removed and are obtained succinic acid fluorine-containing alcohol ester A, and structural formula is:
(2) the 26.02g sodium hydrogensulfite being made into mass concentration is 25% the aqueous solution, stirs, and solution is faint yellow, is positioned over to prepare in the normal pressure balance dropping funel to drip.
Toward the flat synthetic succinic acid fluorine-containing alcohol ester A of 108.8g previous step that adds of four-hole, add the redistilled water of 15g, begin to add thermal agitation, when temperature is 144 ℃, drip the solution of sodium bisulfite for preparing, dripped 2 hours, and dropwised the back and keep this temperature to react again 10 hours.
Occur wax dress product after reaction finishes, obtain product after filtration, wash products so that wash unreacted ester off, obtains fluorine-containing surfactant repeatedly.
Embodiment 3
(1) in being equipped with the four-hole round bottom 500ml flask of agitator, heating jacket, condenser, nitrogen inlet, water knockout drum and thermometer, adds 630g H (CF
2)
6CH
2(OCH
2CH
2)
2OH, 50g maleic anhydride, 6g p-methyl benzenesulfonic acid and 150ml benzene.Agitating heating refluxes under nitrogen protection, and keeping temperature is 100 ℃ of reactions 12 hours, can judge the progress of reaction according to the amount of the water that produces in the water knockout drum, and reaction finishes the back will be unreacted H (CF by distillation and washing
2)
6CH
2(OCH
2CH
2)
2OH and maleic anhydride are removed and are obtained succinic acid fluorine-containing alcohol ester B, and structural formula is:
(2) the 20.81g sodium hydrogensulfite being made into mass concentration is 30% the aqueous solution, stirs, and solution is faint yellow, is positioned over to prepare in the normal pressure balance dropping funel to drip.
Toward the flat synthetic succinic acid fluorine-containing alcohol ester B of 184g previous step that adds of four-hole, add the redistilled water of 15g, begin to add thermal agitation, when temperature is 120 ℃, drip the solution of sodium bisulfite for preparing, dripped 2 hours, and dropwised the back and keep this temperature to react again 6 hours.
Occur wax dress product after reaction finishes, obtain product after filtration, wash products so that wash unreacted ester off, obtains fluorine-containing surfactant repeatedly.
Embodiment 4
(1) in being equipped with the four-hole round bottom 500ml flask of agitator, heating jacket, condenser, nitrogen inlet, water knockout drum and thermometer, adds 476gH (CF
2)
8CH
2OCH
2CH
2OH, 50g maleic anhydride, 8g p-methyl benzenesulfonic acid and 150ml azeotropic agent dimethylbenzene.Agitating heating refluxes under nitrogen protection, and keeping temperature is 100 ℃ of reactions 10 hours, can judge the progress of reaction according to the amount of the water that produces in the water knockout drum, and reaction finishes the back will be unreacted H (CF by distillation and washing
2)
8CH
2OCH
2CH
2OH and maleic anhydride are removed and are obtained succinic acid fluorine-containing alcohol ester B, and structural formula is:
(2) the 20.81g sodium hydrogensulfite being made into mass concentration is 35% the aqueous solution, stirs, and solution is faint yellow, is positioned over to prepare in the normal pressure balance dropping funel to drip.
Toward the flat synthetic succinic acid fluorine-containing alcohol ester B of 206.4g previous step that adds of four-hole, add the redistilled water of 13g, begin to add thermal agitation, when temperature is 130 ℃, drip the solution of sodium bisulfite for preparing, dripped 1.5 hours, and dropwised the back and keep this temperature to react again 15 hours.
Occur wax dress product after reaction finishes, obtain product after filtration, wash products so that wash unreacted ester off, obtains fluorine-containing surfactant repeatedly.
Embodiment 5
Method according to embodiment 2 prepares fluorine-containing surfactant, and step (1) and step (2) be raw materials used to see Table 1 and table 2 respectively.
Table 1
| Quality (g) | |
| Maleic anhydride | ??50 |
| Quality (g) | |
| ??H(CF 2) 8CH 2OH | ??432 |
| P-methyl benzenesulfonic acid | ??6 |
| Cyclohexane | ??150ML |
Table 2
| Quality (g) | Concentration | |
| Sodium hydrogensulfite | ??20.81 | ??20％ |
| Succinic acid fluorine-containing alcohol ester A | ??188.8 |
Embodiment 6
Method according to embodiment 2 prepares fluorine-containing surfactant, and step (1) and step (2) be raw materials used to see Table 3 and table 4 respectively.
Table 3
| Quality (g) | |
| Maleic anhydride | ??50 |
| ??H(CF 2) 6CH 2OH | ??332 |
| P-methyl benzenesulfonic acid | ??8 |
| Benzene | ??150ml |
Table 4
| Quality (g) | Concentration | |
| Sodium hydrogensulfite | ??20.81 | ??30％ |
| Succinic acid fluorine-containing alcohol ester A | ??148.8 |
Embodiment 7
Method according to embodiment 1 prepares fluorine-containing surfactant, and step (1) and step (2) be raw materials used to see Table 5 and table 6 respectively.
Table 5
| Quality (g) | |
| Maleic anhydride | ??50 |
| ??H(CF 2) 4CH 2OCH 2CH 2OH | ??414 |
| P-methyl benzenesulfonic acid | ??6 |
| Toluene | ??150ml |
Table 6
| Quality (g) | Concentration | |
| Sodium hydrogensulfite | ??20.81 | ??35％ |
| Succinic acid fluorine-containing alcohol ester B | ??126.4 |
Embodiment 8
Method according to embodiment 3 prepares fluorine-containing surfactant, and step (1) and step (2) be raw materials used to see Table 7 and table 8 respectively.
Table 7
| Quality (g) | |
| Maleic anhydride | ??50 |
| ??H(CF 2) 4CH 2(OCH 2CH 2) 2OH | ??320 |
| P-methyl benzenesulfonic acid | ??8 |
| Dimethylbenzene | ??150ml |
Table 8
| Quality (g) | Concentration | |
| Sodium hydrogensulfite | ??20.81 | ??40％ |
| Succinic acid fluorine-containing alcohol ester B | ??144 |
Above-mentioned explanation is not done qualification to flesh and blood of the present invention just in order to explain the present invention, and concrete protection domain is seen claim.
Claims (10)
1. succinic acid fluorine-containing alcohol ester sulfonate surfactant is characterized in that having following structural:
Wherein, n is the integer of 4-8, and m is the integer of 0-2.
2. surfactant according to claim 1 is characterized in that: n=8, m=0,1,2.
3. surfactant according to claim 1 is characterized in that: n=6, m=0,1,2.
4. surfactant according to claim 1 is characterized in that: n=4, m=0,1,2.
5. the preparation method of the described succinic acid fluorine-containing alcohol ester sulfonate surfactant of claim 1 is characterized in that may further comprise the steps:
(1) under the situation of catalyst and azeotropic agent existence, with H (CF
2) nCH
2OH and maleic anhydride add thermal agitation under nitrogen protection, reaction finishes the back and obtains succinic acid fluorine-containing alcohol ester A by distilling and washing to remove for unreacted pure and mild maleic anhydride, and structural formula is
(2) above-mentioned succinic acid fluorine-containing alcohol ester A is joined in the reactor, drip mass concentration then and be 20～40% aqueous solution of sodium bisulfite, reaction at a certain temperature, reaction finishes afterreaction liquid layering or precipitation occurs, obtains succinic acid fluorine-containing alcohol ester sulfonate surfactant through separatory or filtration.
6. preparation method according to claim 5 is characterized in that: H (CF in the step (1)
2) nCH
2The mol ratio of OH and maleic anhydride is 2～4: 1, and described catalyst is a p-methyl benzenesulfonic acid, and consumption is 3-8g, and reaction temperature is 80-140 ℃, and the reaction time is 6-18h.
7. preparation method according to claim 5, it is characterized in that: the mol ratio 1: 1.07～3.3 of amber fluorine-containing alcohol ester A of acid and sodium hydrogensulfite in the step (2), reaction temperature is 92～145 ℃, and the solution of sodium bisulfite dropping time is 1.5～2 hours, dropwises afterreaction 6～18h.
8. the preparation method of the described succinic acid fluorine-containing alcohol ester sulfonate surfactant of claim 1 is characterized in that may further comprise the steps:
(1) under the situation of catalyst and azeotropic agent existence, with H (CF
2) nCH
2O (CH
2CH
2O) m H and maleic anhydride add thermal agitation in nitrogen protection, and reaction finishes the back will remove for unreacted ether and maleic anhydride by distillation and washing and obtain succinic acid fluorine-containing alcohol ester B, and structural formula is
(2) above-mentioned succinic acid fluorine-containing alcohol ester B is joined in the reactor, drip mass concentration then and be 20～40% aqueous solution of sodium bisulfite, reaction at a certain temperature, reaction finishes afterreaction liquid layering or precipitation occurs, obtains succinic acid fluorine-containing alcohol ester sulfonate surfactant through separatory or filtration.
9. preparation method according to claim 8 is characterized in that: maleic anhydride and H (CF in the step (1)
2) nCH
2O (CH
2CH
2O) mol ratio of m H is 1: 2～4, and described catalyst is a p-methyl benzenesulfonic acid, and consumption is 3-8g, and reaction temperature is 80-140 ℃, and the reaction time is 6-18h.
10. preparation method according to claim 8, it is characterized in that: the mol ratio 1: 1.07～3.3 of succinic acid fluorine-containing alcohol ester B and sodium hydrogensulfite in the step (2), reaction temperature is 92～145 ℃, and the solution of sodium bisulfite dropping time is 1.5～2 hours, dropwises afterreaction 6～18h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106008286A (en) * | 2016-05-20 | 2016-10-12 | 济南大学 | Polyethylene glycol-bis-maleic acid ethoxy-dodecafluoro-heptanol ester sodium disulfonate and preparation method thereof and application |
| CN111087328A (en) * | 2019-11-07 | 2020-05-01 | 广州宏茂实业有限公司 | Preparation method of fatty alcohol sulfosuccinic acid monoester disodium salt |
| CN112759537A (en) * | 2020-12-18 | 2021-05-07 | 广东方中高新材料有限公司 | Novel synthesis method of fluorosulfonate surfactant |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1535260B (en) * | 2001-07-25 | 2011-11-23 | 西巴特殊化学品控股有限公司 | Perfluoroalkyl-substituted amines, acids, amino acids and thioether acids |
| CN101385954B (en) * | 2007-10-09 | 2011-04-06 | 东南大学 | Preparation method of high pure succinate surfactants for paper manufacturing industry |
| CN101148581A (en) * | 2007-10-26 | 2008-03-26 | 孙焕泉 | Method for preparing high efficiency gemini type oil displacement agent |
-
2009
- 2009-12-30 CN CN200910256598XA patent/CN101745339B/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106008286A (en) * | 2016-05-20 | 2016-10-12 | 济南大学 | Polyethylene glycol-bis-maleic acid ethoxy-dodecafluoro-heptanol ester sodium disulfonate and preparation method thereof and application |
| CN106008286B (en) * | 2016-05-20 | 2017-11-07 | 济南大学 | Double difluoro enanthol ester disulfonic acid sodium of maleic acid ethyoxyl ten of a kind of polyethylene glycol and its preparation method and application |
| CN111087328A (en) * | 2019-11-07 | 2020-05-01 | 广州宏茂实业有限公司 | Preparation method of fatty alcohol sulfosuccinic acid monoester disodium salt |
| CN112759537A (en) * | 2020-12-18 | 2021-05-07 | 广东方中高新材料有限公司 | Novel synthesis method of fluorosulfonate surfactant |
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