CN101869815A - Preparation of hybrid fluorine-containing surfactant and application in weak cationic fabric three-proof finishing agent - Google Patents
Preparation of hybrid fluorine-containing surfactant and application in weak cationic fabric three-proof finishing agent Download PDFInfo
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Abstract
The invention discloses preparation of hybrid fluorine-containing surfactant and application in a weak cationic fabric three-proof finishing agent. The surface tension of the hybrid fluorine-containing surfactant is 30mNm<-1> in 0.001 weight percent aqueous solution and 24mNm<-1> in 0.01 weight percent aqueous solution. The water repellency of the weak cationic fabric three-proof finishing agent prepared by using the surfactant reaches level-9, the hydrophobic property has no obvious change after 5 times of washing, and the back has no osmosis; and the oil repellency is more than or equal to level-7, and the residual oil repellency is more than or equal to level-5 after 5 times of washing. The finishing agent does not use long-chain fluorine-containing alkylate PFOS/A, adopts perfluorobutyl or perfluorohexyl fluorine-containing monomer, overcomes the defect that the activity of the short-chain fluorine-containing monomer is inferior to that of the PFOS/A by using the 'hybrid' fluorine-containing surfactant, and keeps the performance of the fabric finishing agent close to or even reaching the level of the primary product.
Description
Technical field
The present invention relates to fluorine-containing fabric three-proof finishing agent technical field, particularly the weak cationic fabric three-proof finishing agent for preparing with hybrid fluorine-containing surfactant.
Background technology
It refuses Organic fluoride kind fabric finishing agent water, refuses oil, refuses dirty " three is anti-" effect and all be better than the fabric finishing agent (as shown in table 1) of other types, be the first-elected product type of fabric finishing agent in the market, the emphasis of application is rainproof garment fabric, curtain, work clothes, carpet etc.Companies such as U.S. 3M, DuPont, Japan AGC, Da Jin Development and Production go out the fluorine-containing textile finishing agent product of the multiple trade mark, its product all relates to long chain fluorine-containing alkyl compound (PFOS/A), but PFOS/A takes place any can observedly decomposition under various environment physico chemical factors hardly, has very high biological accumulation and many internal organs of human body toxicity.Studies show that the PFOS/A substitute---perfluoro butyl/hexyl Sulfonates inanimate object body inner accumulated effect, America NI OSH and European Union classify as no obvious dangerous substance with it.
Strict says that fluorine-containing textile finishing agent is to be a base polymer coating material of main film forming substance with the fluororesin.Fluororesin then is to be a resinoid general name that contains more C-F chemical bond in the molecular structure that obtains of elementary cell homopolymerization or copolymerization with the monomer that Fluorine containing olefine or side chain contain the fluorine carbon bond.Fluorine-containing textile finishing agent not only has the effect of refusing water, refusing oil, also has antifouling and decontaminable function.The fabric of putting in order through fluorine-containing textile finishing agent still can keep the original color and luster of fabric, feel, gas permeability, snugness of fit etc., and demonstrate not available oil and rub resistance, the decay resistance refused of general hydro carbons or silicone water repellent, fluorine-containing textile finishing agent is popularized rapidly and popularization.
Table 1 fluorine-containing textile finishing agent and common fabric finishing agent performance are relatively
Annotating: zero good △ is general * and poor
(Perfluoroalkyl acrylate, FA) copolymer is electropositive to cationic perfluoroalkyl acrylate, aspect fabric, the processing of paper waterproof and oilproof, the incomparable advantage of anionic fluoropolymer is arranged.When it is handled surface such as electronegative paper, fabric,, give the two thin characteristic of substrate " hydrophobic, hate oil " simultaneously, have potential using value because electrostatic interaction more helps itself and the combining of substrate.(the C number is when 6-10 in the perfluoroalkyl side chain but because FA monomer autologous density is big, be the wax shape under the normal temperature, need to use organic solvent dissolution), difficult emulsification, reactivity is low, be difficult for spreading at aqueous phase, the preparation of cationic perfluoroalkyl acrylate copolymer is restricted, and many problems have also appearred in the polymerization process, for example polymerization is incomplete, and latex particle is unstable and produce oily layer, Powdered precipitation etc., and polymerization rate waits slowly.
Initial people adopt the method for cationic initiator fragment that cationic characteristic is provided more, and with initator 2, the use of 2 '-azo-2-methyl-propyl amidine-dihydrochloride (V-50) and emulsifying agent OTAC is in the majority in the report.For example Linemann etc. successfully prepares cationic perfluoroalkyl acrylate copolymer emulsion by conventional emulsion polymerization under cationic emulsifier OTAC and cationic initator V-50 acting in conjunction.Jong-Wook Ha etc. prepare PS for nuclear, FA is the cationic perfluoroalkyl acrylate polymer emulsion of the nucleocapsid structure of shell by seeded emulsion polymerization,
Except the initator fragment method, people such as Wang Haiwei then introduce cation group by cationic monomer methylacryoyloxyethyl trimethyl ammonium chloride (DMC) cationic are provided, and adopt emulsifier-free emulsion polymerization to prepare cationic non-soap fluorine-containing acrylic acid ester emulsion.
Find in the people practice that long-chain perfluoroalkyl chain, particularly the perfluoroalkyl acrylate hydrophobic of deriving based on perfluoro capryl (C8), oil repellency can be best, so the FA monomer of C8 class is most widely used in all fluorine-containing textile finishing agents.But the FA monomer advantages of excellent stability of C8 class is double-edged sword as freon CFC, show by all kinds of Monitoring Data, it is one of organic pollution of the difficult degradation found in the world at present, have persistence, bioaccumulation, remote animal migration etc., human and environment are caused lasting impact and harm.Formally come into force to China on November 11st, 2004 " about the Convention of Stockholm of persistence organic pollutant ", in China's underground water, the surface water and seawater, all detect perfluoro capryl and polluted, also do not found any decomposition sign of perfluoro capryl in environment and organism at present.
List of references:
[1]Linemann?R.，Malner?T.，Brandsch?R.，et?al.Latex?blends?of?fluorinated?and?fluorine?freeacrylates：Emulsion?polymerization?and?tapping?mode?atomic?force?microscopy?of?filmformation.Macromolecules，1999，32(6)：1715-1721.
[2] Wang Haiwei, Yuan's buckwheat dragon, Wu Shusen. the synthetic and surface property of cationic fluorochemical acrylate. functional polymer journal, 2007,2:184-192.
[3] Kubo unit Shen. fluorine-containing water and oil repellent agent II: the characteristic of fiber and waterproof processing. printing and dyeing, 1996,22 (4): 40-43.
[4]
S.，Guittard?F.，Guimon?C.，et?al.Synthesis?and?characterization?of?copolymers?basedon?styrene?and?partially?fluorinated?acrylates[J].European?Polymer?Journal，2006，42(3)：702-710.
[5]D?Danino，D?Weihs，R?Zana，M?Abe，et?al.Microstructures?in?the?aqueous?solutions?of?ahybrid?anionic?fluorocarbon/hydrocarbon?surfactant，J?Colloid?Interface?Sci，2003，259：383.
Summary of the invention
The object of the invention provides a kind of novel weak cationic fabric three-proof finishing agent.Avoid and use long chain fluorine-containing alkyl compound PFOS/A, but adopt perfluoro butyl or the perfluoro hexyl class fluorochemical monomer that meets the environment protection health requirement, utilize " hybridization " type fluorine-containing surfactant to overcome the active defective of its short chain fluorochemical monomer, keep the fabric finishing agent performance approaching even reach the existing product level not as PFOS/A.Handle back cotton fabric safety, health and technical performance and require to meet fully standard GB 12799-1991:
1. " hybridization " type fluorine-containing surfactant should reach following performance indications: pH6～8, and dynamic surface tension is～30mN m when recording 0.001% weight percent concentration
-1, dynamic surface tension is～24mN m during 0.01% weight percent concentration
-1
2. carry out hydrophobicity test by the 3M-II-1988 method, initial surface pure water contact angle 〉=130 ° is refused water and is reached 9 grades, wash 5 times after hydrophobicity do not have obvious change, the back side does not have and oozes;
3. adopt FZ/T 01067-1999 method to carry out oil repellency test, initial surface CH
2I
2About 120 ° of contact angle is refused oil 〉=7 grade, wash 5 times after residue refuse oil 〉=5 grade.
Realize the novel weak cationic fabric three-proof finishing agent of the object of the invention, be the emulsion-type weak cationic fabric three-proof finishing agent, avoid and use the long chain fluorine-containing alkyl compound, employing meets the perfluoro butyl or the perfluoro hexyl class fluorochemical monomer of environment protection health requirement, " hybridization " type of utilization fluorine-containing surfactant overcomes the active defective not as PFOS/A of its short chain fluorochemical monomer, keep the fabric finishing agent performance near in addition reach the existing product level, the contact angle of water droplet on the cotton that wherethrough was managed reaches as high as 150 °, and the correlation technique index is as shown in table 2.
Table 2 three anti-environmental protection fabric finishing agent technical indicators
The molecular structure of hybrid fluorine-containing surfactant of the present invention as shown in Equation 1, with containing a carbon fluorine chain and a hydrocarbon chain in a part simultaneously, it not only has the very high capillary ability of the reduction aqueous solution, also can reduce the tension force of oil and water termination simultaneously greatly
In the formula, m=4,8,10,14; N=4,6.
The preparation method of hybrid fluorine-containing surfactant of the present invention carries out according to the following procedure:
In the reaction equation, acid is I
2Perhaps watery hydrochloric acid; Ethanol is an ethanol.
Preparation comprises the steps:
1, by weight percentage, the solvent of 30%-65% is poured in the reactor, be warming up to 110-150 ℃, solvent refluxing 30min; F (the CF that adds simultaneously 15%-30% successively
2)
nSO
2N (C
2H
5) (CH
2)
2OH after the hydrogen iodide of 30%-45% and the catalyst mix of 1%-10% are even, carries out polymerisation in solution 6-12h under 110-150 ℃ of temperature;
2, synthetic: as by weight percentage, the solvent of 30%-65% to be poured in the reactor, be warming up to the solvent refluxing temperature; F (the CF that adds simultaneously 15%-30% successively
2)
nSO
2N (C
2H
5) (CH
2)
2I, the N (C of 30%-45%
2H
5)
2(CH
2)
mAfter OH mixes, carry out polymerisation in solution 24-72h;
Wherein, described solvent is: toluene, dimethylbenzene, dimethyl formamide, acetone, ethanol or butanols;
Described catalyst is: I
2Perhaps watery hydrochloric acid.
The application of " hybridization " of the present invention type fluorine-containing surfactant is characterized in that, is used at preparation weak cation fluorine-containing textile finishing agent, and the preparation method comprises the following steps:
Electric mixer, condenser pipe, N are being housed
2In the four-necked bottle of ingress pipe and thermometer, the deionized water that adds the 65-80% percentage by weight successively, 0.2-1.0% percentage by weight composite emulsifying system, " hybridization " type fluorine-containing surfactant accounts for the 25%-67% of composite emulsifying system gross weight in the composite emulsifying system, the acrylic acid of 0.5%-2% percentage by weight or chloride monomer, 1.5%-5% percentage by weight perfluoroalkyl acrylate, 3%-10% percentage by weight acrylate monomer or methacrylate monomers, 0.1%-0.5% percentage by weight crosslinking agent, add 5%-20% percentage by weight cosolvent, guarantee above-mentioned mixing, add 0.05%-0.2% percentage by weight initator then, be warming up to 70 ℃ and carry out emulsion polymerisation, insulation reaction 3-6h, cool off product.
The weak cation fluorine-containing textile finishing agent is made by the raw material of following weight item:
Perfluoroalkyl acrylate monomer 1.5-5%
(methyl) acrylate monomer 3-10%
Chloride monomer 0.5-2%
Crosslinking agent 0.1-0.5%
Emulsifying agent 0.2-1.0%
Initator 0.05-0.2%
Cosolvent 5-20%
Deionized water 65-80%;
Described chloride monomer comprises: vinyl chloride or vinylidene chloride or p-chloromethyl styrene, or methylacryoyloxyethyl trimethyl ammonium chloride; Described crosslinking agent comprises: hydroxy methyl methacrylate, or nitrogen NMA, or DAAM; Described emulsifying agent comprises: octadecyl trimethylammonium bromide, or polyvinyl alcohol, or AEO, or self-control hybrid fluorine-containing emulsifying agent, and the composite emulsifying system is the combination of mentioned emulsifier; Described initator is 2,2 '-azo-2-methyl-propyl amidine-dihydrochloride or tert-butyl group benzylhydroperoxide; Described cosolvent is an acetone, or isopropyl alcohol, or oxolane.
The present invention is an emulsion-type with the weak cationic fabric three-proof finishing agent of " hybridization " type fluorine-containing surfactant preparation, and its most important composition is a fluoropolymer latex.According to the final designed use difference of polymer, with the floride-free acrylic ester monomer of fluorochemical monomer copolymerization except common acrylic acid methyl esters and butyl ester, outside the methyl esters and butyl ester of methacrylic acid, C
8-18The acrylate of long-chain fatty alcohol, methacrylate also usually is used as comonomer.In order to reduce cost and to give polymer other performance,, also have and in the prescription of fluorinated copolymer, introduce monomers such as vinyl chloride, vinylidene chloride, styrene or acrylonitrile as durability etc.; The introducing of methylol compound and acrylic amide cross-linking monomer thereof on the polymer molecular chain as hydroxyethyl methacrylate and DAAM etc., can effectively improve the durability of polymer.The molecular structure of common fluorine-containing textile finishing agent is shown in 2.
2
Description of drawings
Fig. 1 is the design sketch of 1% percentage by weight fluorine-containing textile finishing agent handling of paper, fabric
Among the figure: A: paper 1% percentage by weight DuPont FC-43 handles; B: before paper applies; C/D: paper 1% percentage by weight self-control sample; E: cotton gauze 1% percentage by weight sample applies.
Fig. 2 is the SEM comparison diagram before and after 1% percentage by weight fluorine-containing textile finishing agent handling of paper, the fabric
Among the figure: a: before grey cloth is handled (complete wetting); B: grey cloth is handled back (142 °); C: before the paper process (109 °); D: after the paper process (129 °).
The specific embodiment
The preparation of " hybridization " type fluorine-containing surfactant
1, by weight percentage, the solvent of 30%-65% is poured in the reactor, be warming up to 110-150 ℃, solvent refluxing 30min; F (the CF that adds simultaneously 15%-30% successively
2)
nSO
2N (C
2H
5) (CH
2)
2OH after the hydrogen iodide of 30%-45% and the catalyst mix of 1%-10% are even, carries out polymerisation in solution 6-12h, solid F (CF under 110-150 ℃ of temperature
2)
nSO
2N (C
2H
5) (CH
2)
2The I yield is higher than 90%;
2, synthetic, by weight percentage, earlier the solvent of 30%-65% is poured in the reactor, be warming up to the solvent refluxing temperature; F (the CF that adds simultaneously 15%-30% successively
2)
nSO
2N (C
2H
5) (CH
2)
2I, the N (C of 30%-45%
2H
5)
2(CH
2)
mAfter OH mixes, carry out polymerisation in solution 24-72h, solid product hybrid fluorine-containing surfactant yield is higher than 80%.
Embodiment 1
The preparation of " hybridization " type fluorine-containing surfactant
At first the solvent of 50% percentage by weight is poured in the reactor, be warming up to about 120 ℃ solvent refluxing 30min; F (the CF that adds simultaneously 15% percentage by weight successively
2)
nSO
2N (C
2H
5) (CH
2)
2OH after the catalyst mix of the hydrogen iodide of 30% percentage by weight and 5% percentage by weight is even, carries out polymerisation in solution 6-12h, solid F (CF under 120 ℃ of temperature
2)
nSO
2N (C
2H
5) (CH
2)
2The I yield is 94.5%; Second step is synthetic, at first the solvent of 55% percentage by weight is poured in the reactor, is warming up to the solvent refluxing temperature; F (the CF that adds simultaneously 15% percentage by weight successively
2)
nSO
2N (C
2H
5) (CH
2)
2I, the N (C of 30% percentage by weight
2H
5)
2(CH
2)
mAfter OH mixes, carry out polymerisation in solution 24h, solid product hybrid fluorine-containing surfactant yield is 85.2%.
Embodiment 2
The preparation of " hybridization " type fluorine-containing surfactant
At first the solvent of 35% percentage by weight is poured in the reactor, be warming up to 110 ℃, solvent refluxing 30min; F (the CF that adds simultaneously 15% percentage by weight successively
2)
nSO
2N (C
2H
5) (CH
2)
2OH after the catalyst mix of the hydrogen iodide of 45% percentage by weight and 5% percentage by weight is even, carries out polymerisation in solution 6-12h, solid F (CF under 110 ℃ of temperature
2)
nSO
2N (C
2H
5) (CH
2)
2The I yield is 95.2%; Second step is synthetic, at first the solvent of 40% percentage by weight is poured in the reactor, is warming up to the solvent refluxing temperature; F (the CF that adds simultaneously 15% percentage by weight successively
2)
nSO
2N (C
2H
5) (CH
2)
2I, the N (C of 45% percentage by weight
2H
5)
2(CH
2)
mAfter OH mixes, carry out polymerisation in solution 24h, solid product hybrid fluorine-containing surfactant yield is 89.4%.
Embodiment 3
The preparation of " hybridization " type fluorine-containing surfactant
At first the solvent of 35% percentage by weight is poured in the reactor, be warming up to 150 ℃, solvent refluxing 30min; F (the CF that adds simultaneously 30% percentage by weight successively
2)
nSO
2N (C
2H
5) (CH
2)
2OH after the catalyst mix of the hydrogen iodide of 30% percentage by weight and 5% percentage by weight is even, carries out polymerisation in solution 12h, solid F (CF under 150 ℃ of temperature
2)
nSO
2N (C
2H
5) (CH
2)
2The I yield is 91.2%; Second step is synthetic, at first the solvent of 55% percentage by weight is poured in the reactor, is warming up to the solvent refluxing temperature; F (the CF that adds simultaneously 15% percentage by weight successively
2)
nSO
2N (C
2H
5) (CH
2)
2I, the N (C of 30% percentage by weight
2H
5)
2(CH
2)
mAfter OH mixes, carry out polymerisation in solution 24-72h, solid product hybrid fluorine-containing surfactant yield is 84.6%.
Embodiment 4
Employing is hung the sheet method and measure certain density hybrid fluorine-containing surfactant aqueous solution dynamic surface tension at ambient temperature on German Kruss K12 type interfacial tensimeter, and water is deionized water.
The hybrid fluorine-containing surfactant that recrystallizing and refining is handled among the embodiment 1 is got and is dissolved in the deionized water standing over night in right amount.Dynamic surface tension is～30mN m when recording 0.001% weight percent concentration
-1, dynamic surface tension is～24mN m during 0.01% weight percent concentration
-1
Application example 1:
Electric mixer, condenser pipe, N are being housed
2In the four-necked bottle of ingress pipe and thermometer, add deionized water 120mL successively, 0.36g octadecyl trimethylammonium bromide, 0.20g OS and 0.10g " hybridization " type fluorine-containing surfactant, 1.0g acrylic acid fully dissolves.3.0g perfluoroalkyl acrylate, 6.0g methacrylic acid stearyl monomer at first are dissolved in the 20mL acetone, mix the back with 10.0g methyl methacrylate and an amount of hydroxyethyl methacrylate etc. then and add.Logical N
2Deoxygenation, 45 ℃ of following high speed machines stir 30min.Add initator 2,2 '-azo-2-methyl-propyl amidine-dihydrochloride (AIBA) aqueous solution (0.2gAIBA/20mL H
2O), be warming up to initiation more than 70 ℃.After temperature-rise period finishes, in 73 ℃ of left and right sides insulation reaction 3-6h.The discharging emulsion solid content is 11.25wt%.
In this example " hybridization " type fluorine-containing surfactant molecular structure as shown in Equation 1, m=4,8,10,14; N=4,6.Perfluoroalkyl acrylate monomer perfluoroalkyl side chain comprises following structure :-CF2CF2CF2CF3 ,-CF2CF2CF2CF2CF2CF3 ,-CF2CFHCF3 ,-CF (CF3) CFHCF (CF3) CF3.
Embodiment 6
Application example 2:
Electric mixer, condenser pipe, N are being housed
2In the four-necked bottle of ingress pipe and thermometer, add deionized water 200mL successively, 0.8g homemade " hybridization " type fluorine-containing surfactant, 0.4g polyvinyl alcohol and 2.0g acrylic acid fully dissolve.5.0g perfluoroalkyl acrylate, 10.0g methacrylic acid stearyl monomer at first are dissolved in the 30mL acetone, mix the back with 25.0g methyl methacrylate and an amount of hydroxy methyl methacrylate or nitrogen NMA etc. then and add.Logical N
2Deoxygenation, high speed machine stirs 30min.Add initator 2,2 '-azo-2-methyl-propyl amidine-dihydrochloride (AIBA) aqueous solution (0.3gAIBA/20mL H
2O), be warming up to initiation more than 70 ℃.After temperature-rise period finishes,, add 0.1g initiator A IBA and continue reaction 2-3h in 73 ℃ of left and right sides insulation reaction 3h.The discharging emulsion solid content is 14.69wt%.
In this example " hybridization " type fluorine-containing surfactant molecular structure as shown in Equation 1, m=4,8,10,14; N=4,6.Perfluoroalkyl acrylate monomer perfluoroalkyl side chain comprises following structure :-CF2CF2CF2CF3 ,-CF2CF2CF2CF2CF2CF3 ,-CF2CFHCF3 ,-CF (CF3) CFHCF (CF3) CF3.
Embodiment 7
Application example 3:
Electric mixer, condenser pipe, N are being housed
2In the four-necked bottle of ingress pipe and thermometer, add deionized water 220mL successively, 0.8g homemade " hybridization " type fluorine-containing surfactant, 0.4g polyvinyl alcohol and 1.0g acrylic acid, 1.0g methylacryoyloxyethyl trimethyl ammonium chloride fully dissolves.10.0g perfluoroalkyl acrylate, 15.0g methacrylic acid stearyl monomer at first are dissolved in the 40mL acetone, then with 30.0g methyl methacrylate and an amount of crosslinking agent (hydroxy methyl methacrylate, or nitrogen NMA, or DAAM) etc. mixing the back adds.Logical N
2Deoxygenation, high speed machine stirs 30min, ultrasonic homogeneous 15min.Add initator tert-butyl group benzylhydroperoxide 0.4g, be warming up to more than 70 ℃ and cause.After temperature-rise period finishes,, add 0.2g initiator A IBA and continue reaction 2-3h in 73 ℃ of left and right sides insulation reaction 3h.The discharging emulsion solid content is 14.69wt%.
In this example " hybridization " type fluorine-containing surfactant molecular structure as shown in Equation 1, m=4,8,10,14; N=4,6.Perfluoroalkyl acrylate monomer perfluoroalkyl side chain comprises following structure :-CF2CF2CF2CF3 ,-CF2CF2CF2CF2CF2CF3 ,-CF2CFHCF3 ,-CF (CF3) CFHCF (CF3) CF3.
Embodiment 8
The waterproof and oilproof test:
Get 10 * 10cm
2Embryo cloth or paper be soaked in 1wt% fluorine-containing textile finishing agent 2h, take out the dried unnecessary finishing agent raffinate that is attached to embryo cloth or paper surface of control, hang nature and dry.The 3-5min that anneals under 160 ℃ of high temperature then is in order to test.
1. hydrophobicity test
Press the test of 3M-II-1988 method.The mixture of preparing a series of isopropyl alcohols and water drops in solvent on the textile sample as test solvent, observes its wetting situation and decides.The grade of hydrophobic grade drop correspondence just at the highest level.Hydrophobicity is divided 12 grades, with 12 grades for the highest.
2. oil repellency test
Adopt the test of FZ/T 01067-1999 method.It is the liquid homologue that reduces successively with 8 kinds of surface tension as standard, respectively various standard test solutions are dropped on the fabric face with dropper, observe its wetting situation and decide.The progression of at last not wetting alkane correspondence is the oily progression of hating of test fabric.Hate 8 grades of oily fractions, with the 8th grade for the highest.
This fabric finishing agent is used for the surface treatment of fabric and paper, and compares (A) with U.S. DuPont like product FC-43, as shown in Figure 1 and Figure 2.Paper is after 1wt% fluorine-silicon copolymer thing emulsion is handled, and its surperficial hydrophobicity performance obviously increases (B), and water droplet is spherical in shape in its surperficial self-constriction, very easily rolls (C, D), and its hydrophobic effect meets or exceeds the level of external like product.And common gauze is after 1wt% fluorine-silicon copolymer thing emulsion is handled, and its surface tension obviously descends, but the water liquid of support certain mass non-leakage (E).
Claims (5)
1. " hybridization " type fluorine-containing surfactant is characterized in that having as shown in the formula 1 molecular structure,
M=4 in the formula, 8,10,14; N=4,6.
2. the preparation method of claim 1 described " hybridization " type fluorine-containing surfactant is characterized in that, carries out according to the following procedure:
In the reaction equation, acid is I
2Perhaps watery hydrochloric acid; Ethanol is an ethanol.
3. the preparation method of " hybridization " as claimed in claim 2 type fluorine-containing surfactant is characterized in that, comprises the steps:
1), by weight percentage, the solvent of 30%-65% is poured in the reactor, be warming up to 110-150 ℃, solvent refluxing 30min; F (the CF that adds simultaneously 15%-30% successively
2)
nSO
2N (C
2H
5) (CH
2)
2OH after the hydrogen iodide of 30%-45% and the catalyst mix of 1%-10% are even, carries out polymerisation in solution 6-12h under 110-150 ℃ of temperature;
2), by weight percentage, the solvent of 30%-65% is poured in the reactor, be warming up to the solvent refluxing temperature; F (the CF that adds simultaneously 15%-30% successively
2)
nSO
2N (C
2H
5) (CH
2)
2I, the N (C of 30%-45%
2H
5)
2(CH
2)
mAfter OH mixes, carry out polymerisation in solution 24-72h;
Wherein, described solvent is: toluene, dimethylbenzene, dimethyl formamide, acetone, ethanol or butanols;
Described catalyst is: I
2Perhaps watery hydrochloric acid.
4. the application of claim 1 described " hybridization " type fluorine-containing surfactant is characterized in that, be used to prepare the weak cation fluorine-containing textile finishing agent, described fluorine-containing textile finishing agent has as shown in the formula the molecular structure shown in 2,
5. the application of claim 1 described " hybridization " type fluorine-containing surfactant is characterized in that be used to prepare the weak cation fluorine-containing textile finishing agent, the method for preparing the weak cation fluorine-containing textile finishing agent comprises the following steps:
Electric mixer, condenser pipe, N are being housed
2In the four-necked bottle of ingress pipe and thermometer, by weight percentage, the deionized water that adds 65%-80% successively, 0.2%-1.0% composite emulsifying system, " hybridization " type fluorine-containing surfactant accounts for the 25%-67% of composite emulsifying system gross weight in the composite emulsifying system, the acrylic acid of 0.5%-2% or chloride monomer, 1.5%-5% perfluoroalkyl acrylate, 3%-10% acrylate monomer or methacrylate monomers, the 0.1%-0.5% crosslinking agent, add the 5%-20% cosolvent, guarantee above-mentioned mixing, add the 0.05%-0.2% initator then, be warming up to 70 ℃ and carry out emulsion polymerisation, insulation reaction 3-6h, cool off product
Described chloride monomer comprises: vinyl chloride or vinylidene chloride or p-chloromethyl styrene, or methylacryoyloxyethyl trimethyl ammonium chloride; Described crosslinking agent comprises: hydroxy methyl methacrylate, or nitrogen NMA, or DAAM; Described emulsifying agent comprises: octadecyl trimethylammonium bromide, or polyvinyl alcohol, or AEO, or hybrid fluorine-containing emulsifying agent, and the composite emulsifying system is the combination of mentioned emulsifier; Described initator is 2,2 '-azo-2-methyl-propyl amidine-dihydrochloride or tert-butyl group benzylhydroperoxide; Described cosolvent is an acetone, or isopropyl alcohol, or oxolane.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115160486A (en) * | 2022-07-29 | 2022-10-11 | 同济大学 | Antibacterial fluorine-containing emulsifier and preparation method thereof |
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| WO2003010128A2 (en) * | 2001-07-25 | 2003-02-06 | Ciba Specialty Chemicals Holding Inc. | Perfluoroalkyl-substituted amines, acids, amino acids and thioether acids |
| CN1826053A (en) * | 2003-07-23 | 2006-08-30 | 拜尔农作物科学股份公司 | Fungicidal active substance combinations |
| CN101406816A (en) * | 2008-10-31 | 2009-04-15 | 浙江工业大学 | Method for producing sulfuric acid fluorinated surfactants |
| CN101502771A (en) * | 2009-02-12 | 2009-08-12 | 中国海洋石油总公司 | Fluorocarbon gemini surfactant as well as preparation method and application thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003010128A2 (en) * | 2001-07-25 | 2003-02-06 | Ciba Specialty Chemicals Holding Inc. | Perfluoroalkyl-substituted amines, acids, amino acids and thioether acids |
| CN1535260A (en) * | 2001-07-25 | 2004-10-06 | �������⻯ѧƷ�ع�����˾ | Perfluoroalkyl-substituted amines, acids, amino acids and thioether acids |
| CN1826053A (en) * | 2003-07-23 | 2006-08-30 | 拜尔农作物科学股份公司 | Fungicidal active substance combinations |
| CN101406816A (en) * | 2008-10-31 | 2009-04-15 | 浙江工业大学 | Method for producing sulfuric acid fluorinated surfactants |
| CN101502771A (en) * | 2009-02-12 | 2009-08-12 | 中国海洋石油总公司 | Fluorocarbon gemini surfactant as well as preparation method and application thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115160486A (en) * | 2022-07-29 | 2022-10-11 | 同济大学 | Antibacterial fluorine-containing emulsifier and preparation method thereof |
| CN115160486B (en) * | 2022-07-29 | 2023-11-03 | 同济大学 | Antibacterial fluorine-containing emulsifier and preparation method thereof |
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| CN101869815B (en) | 2012-11-21 |
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