CN108329228B - Perfluoro polyether amide propyl quaternary ammonium salt containing hydroxyalkyl and preparation method thereof - Google Patents
Perfluoro polyether amide propyl quaternary ammonium salt containing hydroxyalkyl and preparation method thereof Download PDFInfo
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Abstract
A perfluoroalkyl polyether amidopropyl quaternary ammonium salt containing hydroxyalkyl is characterized in that the molecular formula is as follows:
wherein n is 1 to 20; r is- (CH)2)mCH2OH, m is 1 to 5; and X is Cl or Br. The product of the invention has no toxicity, good water solubility and high surface activity.
Description
Technical Field
The invention particularly relates to a perfluoropolyether amidopropyl quaternary ammonium salt containing hydroxyalkyl and a preparation method thereof.
Background
Technical Field
The fluorine surfactant is an important special surfactant, has the highest surface activity in all the surfactants at present, is also called as a super surfactant and has special properties which cannot be compared with other surfactants. Therefore, the fluorine surfactant can be used for enhancing the product performance in the field of common surface activity, such as printing ink, coating, washing, oil extraction and the like, and can also be applied to aspects of fluorine protein foam extinguishing agents, electroplating inhibitors, fabric finishing agents and the like. However, conventional fluorosurfactants such as perfluorooctylsulfonyl fluoride, perfluorooctanesulfonic acid and its salts and various related derivatives (collectively referred to as PFOS) are classified as Persistent Organic Pollutants (POPs) due to their non-susceptibility to degradation in nature, bioaccumulation in the food chain, and toxicity to humans and animals, and the national convention of human committee for review approval of the stockholm convention on persistent organic pollutants on 8/30 2013 further limits their use.
The perfluoropolyether surfactant is a novel fluorine surfactant, has the characteristics of good water solubility, high surfactant, strong wettability, degradability, environmental friendliness and the like, and is called an effective substitute for replacing the traditional fluorine surfactant in some fields. The U.S. environmental protection agency has reviewed and agreed upon products of perfluoropoly ether salts from a foreign company, and such products have also passed U.S. FDA and germany BFR certification for food contact. The synthesized perfluoropolyether derivative sulfonate type perfluoro surfactant is prepared by four-step reaction in Zhou Ji Hua, the lowest surface tension value and the cmc value of the synthesized perfluoropolyether derivative sulfonate type perfluoro surfactant are respectively 20.03mN/m and 1.34 x 10 < -4 > g/L (Zhou Ji Hua Mengwang, yellow flame root, synthesis and performance of the perfluoropolyether derivative sulfonate type fluorocarbon surfactant, printing and dyeing auxiliary agent 2014,1(31): 9-12). The preparation process of the perfluoropolyether surfactant needs four steps, has low yield and is not beneficial to industrial production.
Disclosure of Invention
The invention aims to provide a perfluoropolyether amidopropyl quaternary ammonium salt containing hydroxyalkyl and a preparation method thereof.
In the invention, under the condition that triethylamine is used as an acid-binding agent, perfluoropolyether amidopropyl dimethyl tertiary amine is prepared through amidation reaction; the perfluoropolyether amidopropyl dimethyl tertiary amine and the halohydrin are quaternized in the solvent to obtain the product of the perfluoropolyether amidopropyl quaternary ammonium salt containing hydroxyalkyl. The preparation method is simple and has three steps of reaction, the product has high purity, good wettability and high surfactant and has better water solubility compared with the traditional fluorine surfactant.
The molecular formula of the hydroxyalkyl-containing perfluoropolyether amidopropyl quaternary ammonium salt is shown as follows:
wherein n is 1 to 20; r is- (CH)2)mCH2OH, m is 1 to 5; x is Cl or Br.
The boundary micelle concentration of the novel perfluoro polyether amide propyl quaternary ammonium salt containing hydroxyalkyl is 10-4-10- 5mol/L; has high surface activity and the lowest surface tension of 20-16 mN/m; and has good wettability, and the contact angle of the liquid crystal on the parafilm reaches 0 DEG, so that the liquid crystal can be completely spread on the parafilm.
The invention relates to a preparation method of perfluoropolyether amidopropyl quaternary ammonium salt containing hydroxyalkyl, which comprises the following steps:
firstly, adding triethylamine and N, N-dimethyl-1, 3-propane diamine into a solvent, slowly dripping perfluoropolyether acyl fluoride into the mixed solution for 1 to 2 hours at the temperature of between 0 and 5 ℃, stirring, returning to the room temperature, and heating to the temperature of between 40 and 50 ℃ for reaction for 3 to 4 hours; removing the solvent and unreacted substances by rotary evaporation, and washing for 3-5 times by using three times of water to prepare perfluoropolyether amidopropyl dimethyl tertiary amine;
secondly, carrying out quaternization reaction on perfluoropolyether amidopropyl dimethyl tertiary amine and halohydrin under the conditions of solvent and heating to obtain a crude product perfluoropolyether amidopropyl quaternary ammonium salt;
thirdly, removing the solvent and the unreacted halohydrin from the crude product prepared in the second step through suction filtration, and drying to obtain a waxy target product.
In the first step of reaction process, the solvent is diethyl ether, ethyl acetate or isopropanol, the addition amount of the solvent is 10-20 times of the volume of reactants, and the molar ratio of the perfluoropolyether acyl fluoride to the N, N-dimethyl-1, 3-propane diamine to the triethylamine is 1: 1: 1-5, the initial reaction temperature is 0-5 ℃, the reaction time is 1-2 hours, and then the reaction is carried out for 3-4 hours under the condition of heating to 40-50 ℃.
The structural formula of the perfluoropolyether acyl fluoride in the first step of synthesis is as follows:
wherein n is an integer from 1 to 20;
in the second step of reaction, the solvent is selected from isopropanol or ethanol, the dosage of the isopropanol or ethanol is 10-20 times of the total volume of the perfluoropolyether amidopropyl dimethyl tertiary amine and the halohydrin, the molar ratio of the perfluoropolyether amidopropyl dimethyl tertiary amine to the halohydrin is 1:1.1-2, the reaction temperature is 50-70 ℃, and the reaction time is 5-10 hours.
The structural formula of the intermediate perfluoropolyether amidopropyl dimethyl tertiary amine generated in the second step of synthesis process is as follows:
wherein n is an integer from 1 to 20;
the structural formula of the halohydrin in the second step of reaction process is as follows:
wherein m is an integer of 1-5, and X is Cl or Br.
The hydroxyalkyl-containing perfluoropolyether amidopropyl quaternary ammonium salt product is yellow colloidal solid.
The perfluorinated surfactant can be used as a wetting agent of printing ink and pesticide; can be used for protein foam extinguishing agent.
The invention has the following technical effects:
firstly, the synthesis yield of the synthesized hydroxyalkyl-containing perfluoropolyether amidopropyl quaternary ammonium salt is 88 to 96 percent, and the yield of the Zhoujihua perfluoropolyether derived sulfonate fluorocarbon surfactant is 50 to 65 percent.
Secondly, the synthesized perfluoropolyether amidopropyl quaternary ammonium salt containing hydroxyalkyl has oxygen atoms in a hydrophobic group and a hydrophilic group, so that the synthesized perfluoropolyether amidopropyl quaternary ammonium salt has good water solubility, overcomes the defect of poor water solubility of the traditional fluorine surfactant mainly derived from perfluorooctanoic acid, and has the solubility which is 3-10 times that of the traditional perfluorocarbon based surfactant when the fluorocarbon chains are the same;
third, the quaternizing agent halohydrin of the present invention is more environmentally friendly than the high surfactant quaternizing agent methyl iodide of conventional cationic perfluoroalkyl surfactants.
Fourthly, the synthesized perfluoropolyether amidopropyl quaternary ammonium salt containing hydroxyalkyl has high surfactant of the traditional fluorosurfactant and bactericidal property, and the killing rate of 10min on staphylococcus aureus (ATCC-6538) and escherichia coli (ATCC-8099) is 95.0-99.6 percent and 95.3-99.0 percent respectively.
Fifthly, compared with the traditional fluorine surfactant, the synthesized perfluoro polyether amidopropyl quaternary ammonium salt containing hydroxyalkyl is easy to degrade, the primary degradation rate of the product can reach 88.2% -99.4%, the product can not be accumulated along with food chains in organisms, and the product can replace part of the traditional fluorine surfactant in the industrial field.
Description of the drawings:
FIG. 1 is an infrared spectrum of a hydroxyalkyl-containing perfluoropolyether amidopropyl quaternary ammonium salt of the present invention. 1050cm can be seen in FIG. 1-1And 1240cm-1The left and right peaks are-CF2An asymmetric stretching vibration peak; the content of the raw materials is 1884cm-1The peak at (A) is shifted to 1710cm in the intermediate and product-1Indicating that the acyl fluoride bond (-COF) in the original is broken to form a new amide bond (-CONH) -), and 3000-3200cm in the intermediate and the product-1(ii) a vibrational spectrum having a peak at-NH; 3650cm in the product-1To 3350cm-1Scope indicates-CH2The existence of OH indicates the success of the synthesis.
FIG. 2 is a surface tension map of a hydroxyalkyl-containing perfluoropolyether amidopropyl quaternary ammonium salt of the present invention. From FIG. 2, it can be seen that the surfactant can reduce the surface tension of water from 72mN/m to 18mN/L, and the critical micelle concentration of the aqueous solution is reached at 0.024mmol/L, which shows that the product shows extremely high surface activity from the surface tension reducing capability and the effect.
Detailed Description
Example 1:
raw materials and dosage
9.96g of oligomeric perfluoropolyether acyl fluoride (N ═ 1) compound, 2.24g of N, N-dimethyl-1, 3-propanediamine, 2.22g of triethylamine, 1.61g of chloroethanol, 30ml of dehydrated ether and 40ml of isopropanol, respectively;
(II) specific preparation method
Firstly, the triethylamine and the N, N-dimethyl-1, 3-propane diamine are added into anhydrous ether according to the proportion, perfluoropolyether acyl fluoride is slowly dripped into the mixed solution under the condition of 0 ℃ and stirred, after 1 hour, the mixed solution is dripped off, the mixed solution is returned to the room temperature, and then the mixed solution is heated to 40 ℃ for reaction for 3 hours; removing the solvent and unreacted substances by rotary evaporation, and washing for 3 times by using water for three times to prepare an intermediate; and putting the intermediate and chloroethanol into isopropanol according to the mass ratio, heating to 50 ℃, reacting for 5 hours, and removing the solvent and unreacted quaternizing agent by rotary evaporation to obtain yellow colloidal solid, namely the product perfluoropolyether amidopropyl quaternary ammonium salt, wherein the yield is 96%.
The product measured by a K12 surface tension meter can reduce the surface tension of water from 72mN/m to 17.7mN/m, and can also reduce the contact angle of water on a paraffin film from 105 degrees to 0 degrees, and completely wet a hydrophobic surface. The primary biodegradation degree of the product is 90.0%, and the killing rate of the product on staphylococcus aureus (ATCC-6538) and escherichia coli (ATCC-8099) for 10min is 98.0% and 99.0% respectively.
Example 2:
raw materials and dosage
30.54g of an oligomeric perfluoropolyether acid fluoride (N ═ 8) compound, 1.84g of N, N-dimethyl-1, 3-ethylenediamine, 2.22g of triethylamine, 1.61g of chloroethanol, 50ml of ethyl acetate and 60ml of absolute ethanol, respectively; (II) specific preparation method
Firstly, the triethylamine and the N, N-dimethyl-1, 3-ethylenediamine are added into ethyl acetate according to the proportion, perfluoropolyether acyl fluoride is slowly dripped into the mixed solution under the condition of 3 ℃ and stirred, after 1.5 hours, the mixture is dripped off, then the temperature returns to the room temperature, and the mixture is heated to 50 ℃ for reaction for 4 hours; removing the solvent and unreacted substances by rotary evaporation, and washing for 5 times by using three times of water to prepare an intermediate; and putting the intermediate and chloroethanol into absolute ethyl alcohol according to the mass ratio, heating to 60 ℃, reacting for 8 hours, and performing rotary evaporation to remove low-boiling-point substance impurities to obtain a yellow colloidal solid, namely the product perfluoropolyether amidopropyl quaternary ammonium salt, wherein the yield is 92%.
The product measured by a K12 surface tension meter can reduce the surface tension of water from 72mN/m to 17.1mN/m, and can also reduce the contact angle of water on a paraffin film from 105 degrees to 0 degrees, and completely wet a hydrophobic surface. The product has primary biodegradation degree of 89.7%, and killing rate of Staphylococcus aureus (ATCC-6538) and Escherichia coli (ATCC-8099) for 10min of 98.7% and 98.5%
Example 3:
raw materials and dosage
An oligomeric perfluoropolyether acid fluoride (N ═ 15) compound 51.12g, N-dimethyl-1, 3-propanediamine 2.24g, triethylamine 2.22g, 5-bromo-1-pentanol 3.34g, 60ml and 60ml of dehydrated ether and isopropanol, respectively;
(II) specific preparation method
Firstly, the triethylamine and the N, N-dimethyl-1, 3-propane diamine are added into anhydrous ether according to the proportion, perfluoropolyether acyl fluoride is slowly dripped into the mixed solution under the condition of minus 0 ℃ and stirred, after 1 hour, the mixed solution is dripped off, the mixed solution is returned to the room temperature, and then the mixed solution is heated to 45 ℃ for reaction for 4 hours; removing the solvent and unreacted substances by rotary evaporation, and washing for 4 times by using three times of water to prepare an intermediate; and putting the intermediate and 5-bromo-1-pentanol into absolute ethyl alcohol according to the mass ratio, heating to 65 ℃, reacting for 7 hours, and performing rotary evaporation to remove impurities of low-boiling-point substances to obtain yellow colloidal solid, namely the product perfluoropolyether amidopropyl quaternary ammonium salt, wherein the yield is 95%.
The product measured by a K12 surface tension meter can reduce the surface tension of water from 72mN/m to 17.6mN/m, and can also reduce the contact angle of water on a paraffin film from 105 degrees to 13 degrees, and can wet a hydrophobic surface. The primary biodegradation degree of the product is 90.1%, and the killing rate of the product on staphylococcus aureus (ATCC-6538) and escherichia coli (ATCC-8099) for 10min is 98.5% and 98.1%, respectively.
Example 4:
raw materials and dosage
An oligomeric perfluoropolyether acid fluoride (N ═ 20) compound 65.82g, N-dimethyl-1, 3-propanediamine 2.24g, triethylamine 4.24g, chlorohydrin 1.61g, ethyl acetate and isopropanol 40ml and 50ml, respectively; (II) specific preparation method
Firstly, the triethylamine and the N, N-dimethyl-1, 3-propane diamine are added into ethyl acetate according to the proportion, and the perfluoropolyether acyl fluoride is slowly dripped into the mixed solution for stirring at the temperature of 5 ℃. After 2 hours, the mixture is dripped off, the temperature is returned to the room temperature, the mixture is heated to 50 ℃, and the reaction is carried out for 4 hours; removing the solvent and unreacted substances by rotary evaporation, and washing for 4 times by using three times of water to prepare an intermediate; and putting the intermediate and chloropropanol into absolute ethyl alcohol according to the mass ratio, heating to 70 ℃, reacting for 10 hours, and performing rotary evaporation to remove low-boiling-point substance impurities to obtain a yellow colloidal solid, namely the product perfluoropolyether amidopropyl quaternary ammonium salt, wherein the yield is 88%.
The product can reduce the surface tension of water from 72mN/m to 16.5mN/m as measured by a K12 surface tension meter, and can also reduce the contact angle of water on a paraffin film from 105 degrees to 20 degrees, and can wet a hydrophobic surface. The primary biodegradation degree of the product is 88.9%, and the killing rate of the product on staphylococcus aureus (ATCC-6538) and escherichia coli (ATCC-8099) for 10min is 99.1% and 97.5%, respectively.
Claims (7)
1. A preparation method of perfluoro polyether amide propyl quaternary ammonium salt containing hydroxyalkyl is characterized by comprising the following steps:
firstly, adding triethylamine and N, N-dimethyl-1, 3-propane diamine into a solvent, slowly dripping perfluoropolyether acyl fluoride into the mixed solution for 1 to 2 hours at the temperature of between 0 and 5 ℃, stirring, returning to the room temperature, and heating to the temperature of between 40 and 50 ℃ for reaction for 3 to 4 hours; removing the solvent and unreacted substances by rotary evaporation, and washing for 3-5 times by using three times of water to prepare perfluoropolyether amidopropyl dimethyl tertiary amine;
the perfluoropolyether acyl fluoride has the structural formula:
wherein n is an integer from 1 to 20;
the structural formula of the perfluoropolyether amidopropyl dimethyl tertiary amine is as follows:
wherein n is an integer from 1 to 20;
secondly, carrying out quaternization reaction on perfluoropolyether amidopropyl dimethyl tertiary amine and halohydrin under the conditions of solvent and heating to obtain a crude product perfluoropolyether amidopropyl quaternary ammonium salt;
the structural formula of the halogenated alcohol is as follows:
wherein m is an integer of 1-5, and X is Cl or Br;
thirdly, removing the solvent and the unreacted halohydrin from the crude product prepared in the second step through suction filtration, and drying to obtain a waxy target product;
the molecular formula of the obtained perfluoroalkyl polyether amidopropyl quaternary ammonium salt containing hydroxyalkyl is as follows:
wherein n is 1 to 20; r is- (CH)2)mCH2OH, m is 1 to 5; and X is Cl or Br.
2. The method for preparing a perfluoroalkyl group-containing perfluoropolyether amidopropyl quaternary ammonium salt according to claim 1, wherein the concentration of micelles in the hydroxyalkyl group-containing perfluoropolyether amidopropyl quaternary ammonium salt is 10-4-10-5mol/L; the lowest surface tension is 20-16mN/m and the contact angle on the parafilm reaches 0 deg.
3. The method for preparing a perfluoroalkyl group-containing perfluoropolyether amidopropyl quaternary ammonium salt as claimed in claim 1, wherein the solvent used in the first step is diethyl ether, ethyl acetate or isopropanol, and the addition amount is 10-20 times the volume of the reactants.
4. The method for preparing a hydroxyalkyl-containing perfluoropolyether amidopropyl quaternary ammonium salt as claimed in claim 1, wherein the first reaction step comprises the following steps: n, N-dimethyl-1, 3-propanediamine: the molar ratio of triethylamine is 1: 1: 1-5.
5. The method for preparing a perfluoroalkyl group-containing perfluoropolyether amidopropyl quaternary ammonium salt according to claim 1, wherein the solvent used in the second reaction step is isopropanol or ethanol, and the amount of the solvent used is 10 to 20 times of the total volume of the perfluoropolyether amidopropyl dimethyl tertiary amine and the halohydrin.
6. The method for preparing a perfluoroalkyl group-containing perfluoropolyether amidopropyl quaternary ammonium salt according to claim 1, wherein the molar ratio of perfluoropolyether amidopropyl dimethyl tertiary amine to halohydrin in the second reaction step is 1: 1.1-2.
7. The method for preparing a perfluoroalkyl group-containing perfluoropolyether amidopropyl quaternary ammonium salt as claimed in claim 1, wherein the reaction temperature in the second step is 50-70 ℃ and the reaction time is 5-10 hours.
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