CN100469431C - Fluorine containing cationic macromolecules emulsifying agent and its preparation method - Google Patents

Fluorine containing cationic macromolecules emulsifying agent and its preparation method Download PDF

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CN100469431C
CN100469431C CNB2007100227265A CN200710022726A CN100469431C CN 100469431 C CN100469431 C CN 100469431C CN B2007100227265 A CNB2007100227265 A CN B2007100227265A CN 200710022726 A CN200710022726 A CN 200710022726A CN 100469431 C CN100469431 C CN 100469431C
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monomer
fluorine
emulsifying agent
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methacrylic acid
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CN101053800A (en
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倪沛红
毛江
张明祖
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Suzhou University
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Abstract

The invention discloses a fluoridebearing amphipathic macromole emulsifying agent and a preparation method thereof, which is characterized in that: using oxygen anionic initiation polymerization method, benzoic alcohol reacts with alkali to get benzyl oxygen anion used as an initiator, and monomer methyl methacrylate, ethyl methacrylate (amino group is replaced by alkyl) and metacrylic acid ester with fluorine, are added in turns to get fluoridebearing amphipathic macromole emulsifying agent by polyreaction. The invention overcomes the disadvantage that regular anionic polymerization need in severe conditions of extremely low temperature and high vacuum. The invention has a fast reaction rate and a high conversion, and the product is pure and easy to be purified.

Description

A kind of fluorine-containing cationic macromolecules emulsifying agent and preparation method thereof
Technical field
The present invention relates to a kind of fluorine-containing cationic macromolecules emulsifying agent, be specifically related to a kind of by the amphipathic triblock polymer of methyl methacrylate with (amino that alkyl replaces) ethyl ester of the methacrylic acid with pH response and methacrylic acid fluorinated ester formation.
Background technology
Big molecule fluorine-containing emulsifier is a kind of amphipathic fluoropolymer.The amphipathic fluoride polymer is to introduce fluoro-containing group or fluorine-containing groups on the basis of traditional amphipathic polymer.Because the special physics and the chemical property of fluorine, therefore than traditional macromole emulsifying agent, big molecule fluorine-containing emulsifier has more advantage, for example: high surface, high heat-resistant stability and high chemical stability, its fluorine-containing alkyl is hydrophobic but also hate oil not only, so fluorine-containing surfactant is the highest a kind of of surface-active in all surface activating agent up to now, just can make the surface tension of water reduce to very low numerical value under the few situation of consumption.Because macromole emulsifying agent has the critical micelle concentration lower than small-molecular emulsifier, therefore, amphipathic nature polyalcohol can use in very wide scope.This type of fluorine-containing macromole emulsifying agent is because its unique character can be widely used in industrial various aspects, for example: paint of coating, paper apply agent, cosmetic industry etc.
At present, reach its maturity for synthetic low-molecular-weight fluorine surfactant, generally be divided into three steps: the at first synthetic fluorocarbons that contains 6～10 carbon atoms, make the fluoro-containing intermediate that is easy to introduce various hydrophilic radicals then, introduce various hydrophilic radicals at last again, make various surfactants.Be applied to the bibliographical information of emulsion polymerisation and few for the synthetic of the amphipathic nature polyalcohol that has fluorine-containing groups and as emulsifying agent.In recent years, for the research of fluorine-containing block polymer, domestic and international research work concentrates on structural design, the synthetic method of fluoropolymer in a large number.In the prior art, for the fluoropolymer of the regular exquisiteness of composite structure, mainly be to utilize living polymerisation process to implement, for example: active anionic polymerization and atom transfer radical polymerization method.Busse K. etc. utilizes active anionic polymerization, has synthesized the amphipathic copolymer of metering system tert-butyl acrylate and methacrylic acid-2-(N-methyl perfluoro butyl sulfoamido) ethyl ester [poly (t-BMA-b-FMA)] (Busse K.; Kressler J.; Macromolecules, 2002,35:178).Yet active anionic polymerization severe reaction conditions, reaction temperature are very low, are difficult to realize industrialization control and production.
Another kind of synthetic method is to adopt ATRP (ATRP).For example: employing ATRP methods such as domestic Han Zhe literary composition have been synthesized metering system tert-butyl acrylate and perfluoroalkyl methacrylate block copolymer (Li.H.; WuP.P.; Han Z.W.; Polymer, 2002,43:4079).The ATRP method has its unique advantage, but its maximum shortcoming is to contain catalyst in the final product, is difficult to remove, and product is impure.
Recently, some bibliographical informations utilize reversible addition-fracture chain transfer (RAFT) polymerization to prepare fluorine-containing block polymer (Rixens B.; Severac R.; Boutevin B.; Lacroix-Desmazes P.; Polymer, 2005,46:3579; ).A.Laschewsky etc. utilize the RAFT polymerization to prepare fluorine-containing amphipathic triblock polymer equally, and studied its self-assembly property (S.Kubowicz, J.-F.Baussard, J.-F.Lutz, A.F.Th ü neman, H.V.Berlepsch, A.Laschewsky, Angew.Chem.Int.Ed.2005,44,5262).Though the RAFT polymerization has characteristics such as reaction condition gentleness, the RAFT reagent that is added in polymerization process (sulfur-bearing thing) can remain in the final polymer, is difficult to remove, and polymer properties is produced certain influence.
Therefore, a kind of novel amphipathic fluoride macromole emulsifying agent is provided, and the preparation method that can obtain pure polymerizate, to help to enrich the fluorine-containing emulsifier kind, the macromole emulsifying agent of function admirable can be provided for preparation fluoropolymer solutions, spinning finishing agent, paper treating agent etc.
Summary of the invention
The object of the invention provides a kind of fluorine-containing cationic macromolecules emulsifying agent, and a kind of preparation method that can obtain clean product is provided simultaneously.
For achieving the above object, the technical solution used in the present invention is: a kind of fluorine-containing cationic macromolecules emulsifying agent, express by following general formula:
Figure C200710022726D00051
In the formula, x is 10～20, and y is 15～60, and z is 5～10,
R 1Be selected from
Figure C200710022726D00061
Or
Figure C200710022726D00062
In a kind of,
R 2Be selected from-CH 2CF 3,-CH 2CF 2CHFCF 3,-CH 2CF 2CF 2CF 2CHF 2,-CH 2CF 2CF 2CF 2CF 2CF 2CHF 2, or-CH 2CF 2CF 2CF 2CF 2CF 2CF 2CF 2CF 2CF 3
The preparation method of above-mentioned fluorine-containing cationic macromolecules emulsifying agent adopts oxygen anion initiated polymerization method, comprises the following steps,
(1) preparation initator: with the oxolane is solvent, make hydrofining with etc. behind the phenmethylol stirring reaction of amount, form the benzyloxy anion, as initator;
(2) initator and first monomer were constituted polymerization system in 1: 10 to 1: 20 with mol ratio, stir, reacted 0.5～1.5 hour, described first monomer is selected from methyl methacrylate;
(3) add second monomer that is equivalent to 15 to 60 times of initators with molar ratio computing, stir, reacted 0.5～1.5 hour, described second monomer is selected from methacrylic acid (amino that alkyl replaces) ethyl ester;
(4) add the 3rd monomer that is equivalent to 5 to 10 times of initators with molar ratio computing, stir, reacted 0.5～1.5 hour, described the 3rd monomer is selected from the methacrylic acid fluorinated ester;
(5) use the methyl alcohol cessation reaction, purify, promptly obtain required amphipathic fluoride emulsifying agent.Technique scheme can be expressed as follows:
Figure C200710022726D00063
In the technique scheme, the structural formula of described first monomers methyl methacrylate is,
Figure C200710022726D00071
The structural formula of the described second monomer methacrylic acid (alkyl replace amino) ethyl ester is,
Figure C200710022726D00072
In the formula, R 1Be selected from
Figure C200710022726D00073
Or
Be methacrylic acid-2-(dimethylamino) ethyl ester (DMAEMA), methacrylic acid-2-(lignocaine) ethyl ester (DEAEMA), methacrylic acid-2-(diisopropylaminoethyl) ethyl ester (DPAEMA) or methacrylic acid (tert-butyl group amino) ethyl ester (BAEMA).
The fluorine ester contained structural formula of described the 3rd monomer methacrylic acid is,
Figure C200710022726D00075
In the formula, R 2Be selected from
-CH 2CF 3,-CH 2CF 2CHFCF 3,-CH 2CF 2CF 2CF 2CHF 2,-CH 2CF 2CF 2CF 2CF 2CF 2CHF 2, or-CH 2CF 2CF 2CF 2CF 2CF 2CF 2CF 2CF 2CF 3
Be methacrylic acid-(2,2, the 2-trifluoro) ethyl ester (TFEMA), methacrylic acid-(2,2,3,4,4, the 4-hexafluoro) butyl ester (HFBMA), methacrylic acid-(2,2,3,3,4,4,5,5-octafluoro) pentyl ester (OFPMA), methacrylic acid-(2,2,3,3,4,4,5,5,6,6,7,7-ten difluoros) heptyl ester (DDFHMA), methacrylic acid-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-19 fluorine) ester in the last of the ten Heavenly stems (NDFDMA).
In the technique scheme, when generating initator, must keep alcohol and sylvite reaction with same mole.If alcohol is excessive, can in product, there be the pollution of alcohol, if sylvite is excessive, because K +H -Be alkaline, can the trigger monomer reaction form double activity center, cause the pollution of homopolymers.
In the technique scheme, described purification processes is, steams to remove at 60～70 ℃ of backspins and desolvates, continue to carry out deposition and purification with cold n-hexane, triplicate, at last 40～50 ℃ of vacuum drying to constant weight.
When actual fabrication, for guaranteeing degree of purity of production, can make with extra care raw material earlier, its method is to use the alkaline Al of activation before methyl methacrylate and methacrylic acid-2-(dimethylamino) ethyl ester uses 2O 3Post is handled, and uses CaH then 2More than the dry 12h, at high-purity N 2Carry out decompression distillation under the protection; Hydrofining (KH) is sealed up for safekeeping in mineral oil standby to treat; Solvents tetrahydrofurane (THF) was used potassium hydroxide dry three days, added benzophenone as indicator, carried out anaerobic with the sodium silk and refluxed, and until being darkviolet, steamed before the use; Phenmethylol CaH 2More than the dry 12h, decompression distillation before using.
Because the technique scheme utilization, the present invention compared with prior art has following advantage:
The present invention utilize hydrofining with etc. behind the phenmethylol stirring reaction of amount, form the benzyloxy anion, then according to the length (hydrophobic segment, hydrophilic segment, fluorine-containing groups) of each required segment, the methyl methacrylate, methacrylic acid (amino that alkyl replaces) esters monomer and the fluorine-containing esters monomer of methacrylic acid that add different amounts successively can obtain the fluorine-containing cationic macromolecules emulsifying agent of different structure, different block length.
2. the present invention has overcome the shortcoming that traditional anionic polymerisation need carry out under harsh conditions such as extremely low temperature, high vacuum, and reaction speed is fast, the conversion ratio height, and product is pure, and easy purifying.
3. the present invention's amphipathic nature polyalcohol that will have a temperature and pH response is connected with covalent bond with fluorine-containing section polymer, can improve the character of original amphipathic nature polyalcohol.
The specific embodiment
Below in conjunction with embodiment the present invention is further described:
Embodiment one: PMMA 10-b-PDMAEMA 15-b-POFPMA 5And preparation
(1) preparation of KH: stirring rotator is put into dry reaction bulb in advance, with turned welt rubber stopper jam-pack.Link to each other with vavuum pump with syringe needle, emulsion tube then, charge into high-purity argon gas while vacuumizing, so repeatable operation is three times.After moving into a certain amount of KH in the reaction bulb, inject the THF of 5ml drying with the dry injection device, agitator treating, static back contains the THF of mineral oil with the syringe sucking-off, three times so repeatedly, dries up the THF solution of remnants at last with high-purity argon gas.Utilize the decrement method accurately in the weighing reaction bulb amount of KH (0.2～0.3g about 5.0～7.5mmol).
(2) preparation of initator: a certain amount of THF is expelled in the polymerization bottle that KH is housed.Reaction bulb is inserted in the ice-water bath, magnetic agitation, the phenmethylol (BzOH) of amounts such as injection and KH reacts 0.5～1h simultaneously, KH and BzOH is fully reacted generate benzyl oxygen anion (BzO -).
(3) polymerisation: then in the constant temperature oil bath with 25 ℃ of reaction bulb immigrations, syringe with drying adds first monomers methyl methacrylate (MMA), the mol ratio of controlling first monomer and initator is 10:1, be injected into the first monomer M MA that is equivalent to 10 times of meterings of initator, polymerisation 1～1.5h; The mol ratio of controlling second monomer methacrylic acid-2-(dimethylamino) ethyl ester (DMAEMA) and initator is 15:1, then adds second monomer methacrylic acid-2-(dimethylamino) ethyl ester (DMAEMA) reaction, the 1～1.5h that is equivalent to 15 times of meterings of initator with dry syringe; Control the 3rd monomer methacrylic acid-(2,2,3,3,4,4,5,5-octafluoro) pentyl ester (OFPMA) is 5:1 with the mol ratio of initator, then is equivalent to the 3rd monomer methacrylic acid-(2 of 5 times of meterings of initator with dry syringe adding, 2,3,3,4,4,5, the 5-octafluoro) pentyl ester (OFPMA), reaction 1～1.5h uses dry methyl alcohol cessation reaction at last.Reacted polymer under 60～70 ℃ of conditions, revolves to steam to remove and desolvates, and continues to carry out deposition and purification with cold n-hexane, and triplicate is dried to constant weight for 40～50 ℃ at vacuum drying oven at last.Obtain required product, record productive rate greater than 95%.Product through gel permeation chromatography (GPC) and proton nmr spectra and fluorine spectrum ( 1H NMR, 19F NMR) detects the structure of its molecular weight, molecular weight distribution and copolymer, prove to have obtained target product.
Embodiment two: PMMA 10-b-PDMAEMA 30-b-POFPMA 5And preparation
(1) preparation of KH: identical with embodiment one.
(2) preparation of initator: identical with embodiment one.
(3) polymerisation: then in the constant temperature oil bath with 25 ℃ of reaction bulb immigrations, syringe with drying adds first monomers methyl methacrylate (MMA), the mol ratio of controlling first monomer and initator is 10:1, is injected into the first monomer M MA monomer that is equivalent to 10 times of meterings of initator and carries out polymerisation 1～1.5h; The mol ratio of controlling second monomer methacrylic acid-2-(dimethylamino) ethyl ester (DMAEMA) and initator is 30:1, then adds second monomer methacrylic acid-2-(dimethylamino) ethyl ester (DMAEMA) reaction, the 1～1.5h that is equivalent to 30 times of meterings of initator with dry syringe; Control the 3rd monomer methacrylic acid-(2,2,3,3,4,4,5,5-octafluoro) pentyl ester (OFPMA) is 5:1 with the mol ratio of initator, then is equivalent to the 3rd monomer methacrylic acid-(2 of 5 times of meterings of initator with dry syringe adding, 2,3,3,4,4,5, the 5-octafluoro) pentyl ester (OFPMA), reaction 1～1.5h uses dry methyl alcohol cessation reaction at last.Reacted polymer under 60～70 ℃ of conditions, revolves to steam to remove and desolvates, and continues to carry out deposition and purification with cold n-hexane, and triplicate is dried to constant weight for 40～50 ℃ at vacuum drying oven at last.Obtain required product, record productive rate greater than 95%.Product through gel permeation chromatography (GPC) and proton nmr spectra and fluorine spectrum ( 1H NMR, 19F NMR) detects the structure of its molecular weight, molecular weight distribution and copolymer, prove to have obtained target product.
Embodiment three: PMMA 10-b-PDMAEMA 40-b-POFPMA 10And preparation
(1) preparation of KH: identical with embodiment one.
(2) preparation of initator: identical with embodiment one.
(3) polymerisation: then in the constant temperature oil bath with 25 ℃ of reaction bulb immigrations, syringe with drying adds first monomers methyl methacrylate (MMA), the mol ratio of controlling first monomer and initator is 10:1, is injected into the first monomer M MA monomer that is equivalent to 10 times of meterings of initator and carries out polymerisation 1～1.5h; The mol ratio of controlling second monomer methacrylic acid-2-(dimethylamino) ethyl ester (DMAEMA) and initator is 40:1, then adds second monomer methacrylic acid-2-(dimethylamino) ethyl ester (DMAEMA) reaction, the 1～1.5h that is equivalent to 40 times of meterings of initator with dry syringe; Control the 3rd monomer methacrylic acid-(2,2,3,3,4,4,5,5-octafluoro) pentyl ester (OFPMA) is 10:1 with the mol ratio of initator, then is equivalent to the 3rd monomer methacrylic acid-(2 of 10 times of meterings of initator with dry syringe adding, 2,3,3,4,4,5, the 5-octafluoro) pentyl ester (OFPMA), reaction 1～1.5h uses dry methyl alcohol cessation reaction at last.Reacted polymer under 60～70 ℃ of conditions, revolves to steam to remove and desolvates, and continues to carry out deposition and purification with cold n-hexane, and triplicate is dried to constant weight for 40～50 ℃ at vacuum drying oven at last.Obtain required product, record productive rate greater than 95%.Product through gel permeation chromatography (GPC) and proton nmr spectra and fluorine spectrum ( 1H NMR, 19F NMR) detects the structure of its molecular weight, molecular weight distribution and copolymer, prove to have obtained target product.
Embodiment four: PMMA 20-b-PDMAEMA 60-b-PHFBMA 10And preparation
(1) preparation of KH: identical with embodiment one.
(2) preparation of initator: identical with embodiment one.
(3) polymerisation: then in the constant temperature oil bath with 25 ℃ of reaction bulb immigrations, syringe with drying adds first monomers methyl methacrylate (MMA), the mol ratio of controlling first monomer and initator is 20:1, is injected into the first monomer M MA monomer that is equivalent to 20 times of meterings of initator and carries out polymerisation 1～1.5h; The mol ratio of controlling second monomer methacrylic acid-2-(dimethylamino) ethyl ester (DMAEMA) and initator is 60:1, then adds second monomer methacrylic acid-2-(dimethylamino) ethyl ester (DMAEMA) reaction, the 1～1.5h that is equivalent to 60 times of meterings of initator with dry syringe; Control the 3rd monomer methacrylic acid-(2,2,3,4,4,4-hexafluoro) butyl ester (HFBMA) is 10:1 with the mol ratio of initator, then add the 3rd monomer methacrylic acid-(2 that is equivalent to 10 times of meterings of initator with dry syringe, 2,3,4,4, the 4-hexafluoro) butyl ester (HFBMA), reaction 1～1.5h uses dry methyl alcohol cessation reaction at last.Reacted polymer under 60～70 ℃ of conditions, revolves to steam to remove and desolvates, and continues to carry out deposition and purification with cold n-hexane, and triplicate is dried to constant weight for 40～50 ℃ at vacuum drying oven at last.Obtain required product, record productive rate greater than 95%.Product through gel permeation chromatography (GPC) and proton nmr spectra and fluorine spectrum ( 1H NMR, 19F NMR) detects the structure of its molecular weight, molecular weight distribution and copolymer, prove to have obtained target product.
Embodiment five: PMMA 20-b-PDMAEMA 60-b-PDDFHMA 5And preparation
(1) preparation of KH: identical with embodiment one.
(2) preparation of initator: identical with embodiment one.
(3) polymerisation: then use dry syringe in the constant temperature oil bath with 25 ℃ of reaction bulb immigrations, add first monomers methyl methacrylate (MMA), the mol ratio of controlling first monomer and initator is 20:1, is injected into the first monomer M MA monomer that is equivalent to 20 times of meterings of initator and carries out polymerisation 1～1.5h; The mol ratio of controlling second monomer methacrylic acid-2-(dimethylamino) ethyl ester (DMAEMA) and initator is 60:1, then add second monomer methacrylic acid-2-(dimethylamino) ethyl ester (DMAEMA) that is equivalent to 60 times of meterings of initator, reaction 1～1.5h with dry syringe; Control the 3rd monomer methacrylic acid-(2,2,3,3,4,4,5,5,6,6,7,7-ten difluoros) heptyl ester (DDFHMA) is 5:1 with the mol ratio of initator, then is equivalent to the 3rd monomer methacrylic acid-(2,2 of 5 times of meterings of initator with dry syringe adding, 3,3,4,4,5,5,6,6,7,7-ten difluoros) heptyl ester (DDFHMA), reaction 1～1.5h uses dry methyl alcohol cessation reaction at last.Reacted polymer under 60～70 ℃ of conditions, revolves to steam to remove and desolvates, and continues to carry out deposition and purification with cold n-hexane, and triplicate is dried to constant weight for 40～50 ℃ at vacuum drying oven at last.Obtain required product, record productive rate greater than 95%.Product through gel permeation chromatography (GPC) and proton nmr spectra and fluorine spectrum ( 1H NMR, 19F NMR) detects the structure of its molecular weight, molecular weight distribution and copolymer, prove to have obtained target product.
Embodiment six: PMMA 20-b-PDEAEMA 60-b-PNDFDMA 5And preparation
(1) preparation of KH: identical with embodiment one.
(2) preparation of initator: identical with embodiment one.
(3) polymerisation: then in the constant temperature oil bath with 25 ℃ of reaction bulb immigrations, syringe with drying adds first monomers methyl methacrylate (MMA), the mol ratio of controlling first monomer and initator is 20:1, is injected into the first monomer M MA monomer that is equivalent to 20 times of meterings of initator and carries out polymerisation 1～1.5h; The mol ratio of controlling second monomer methacrylic acid-2-(lignocaine) ethyl ester (DEAEMA) and initator is 60:1, then adds second monomer methacrylic acid-2-(dimethylamino) ethyl ester (DMAEMA) reaction, the 1～1.5h that is equivalent to 60 times of meterings of initator with dry syringe; Control the 3rd monomer methacrylic acid-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-19 fluorine) ester in the last of the ten Heavenly stems (NDFDMA) is 5:1 with the mol ratio of initator, then is equivalent to the 3rd monomer methacrylic acid-(2 of 5 times of meterings of initator with dry syringe adding, 2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-19 fluorine) ester in the last of the ten Heavenly stems (NDFDMA)
Reaction 1～1.5h uses dry methyl alcohol cessation reaction at last.Reacted polymer under 60～70 ℃ of conditions, revolves to steam to remove and desolvates, and continues to carry out deposition and purification with cold n-hexane, and triplicate is dried to constant weight for 40～50 ℃ at vacuum drying oven at last.Obtain required product, record productive rate greater than 95%.Product through gel permeation chromatography (GPC) and proton nmr spectra and fluorine spectrum ( 1H NMR, 19F NMR) detects the structure of its molecular weight, molecular weight distribution and copolymer, prove to have obtained target product.Simultaneously polymer applications is obtained stable functional emulsion in mini-emulsion polymerization.

Claims (5)

1. a fluorine-containing cationic macromolecules emulsifying agent is characterized in that, it is expressed by following general formula:
Figure C200710022726C00021
In the formula, x is 10～20, and y is 15～60, and z is 5～10,
R 1Be selected from
Figure C200710022726C00022
Or
Figure C200710022726C00023
In a kind of;
R 2Be selected from-CH 2CF 3,-CH 2CF 2CHFCF 3,-CH 2CF 2CF 2CF 2CHF 2,-CH 2CF 2CF 2CF 2CF 2CF 2CHF 2, or-CH 2CF 2CF 2CF 2CF 2CF 2CF 2CF 2CF 2CF 3In a kind of.
2. the preparation method of the described fluorine-containing cationic macromolecules emulsifying agent of claim 1 is characterized in that: adopts oxygen anion initiated polymerization method, comprises the following steps,
(1) preparation initator: with the oxolane is solvent, after making hydrofining and waiting the phenmethylol stirring reaction of amount of substance, forms the benzyl oxygen anion, as initator;
(2) initator and first monomer were constituted polymerization system in 1: 10 to 1: 20 with mol ratio, stir, reacted 0.5～1.5 hour, described first monomer is a methyl methacrylate;
(3) add second monomer that is equivalent to 15 to 60 times of initators with molar ratio computing, stir, reacted 0.5～1.5 hour, described second monomer is selected from methacrylic acid (amino that alkyl replaces) ethyl ester;
(4) add the 3rd monomer that is equivalent to 5 to 10 times of initators with molar ratio computing, stir, reacted 0.5～1.5 hour, described the 3rd monomer is selected from the methacrylic acid fluorinated ester;
(5) use the methyl alcohol cessation reaction, purify, promptly obtain required amphipathic fluoride emulsifying agent.
3. the preparation method of fluorine-containing cationic macromolecules emulsifying agent according to claim 2 is characterized in that: the structural formula of described methacrylic acid (amino that alkyl replaces) ethyl ester is,
Figure C200710022726C00031
In the formula, R 1Be selected from
Figure C200710022726C00032
Or
Figure C200710022726C00033
4. the preparation method of fluorine-containing cationic macromolecules emulsifying agent according to claim 2 is characterized in that: the fluorine ester contained structural formula of described methacrylic acid is,
Figure C200710022726C00034
In the formula, R 2Be selected from
-CH 2CF 3,-CH 2CF 2CHFCF 3,-CH 2CF 2CF 2CF 2CHF 2,-CH 2CF 2CF 2CF 2CF 2CF 2CHF 2, or-CH 2CF 2CF 2CF 2CF 2CF 2CF 2CF 2CF 2CF 3
5. the preparation method of fluorine-containing cationic macromolecules emulsifying agent according to claim 2, it is characterized in that: described purification processes is, to continue to carry out deposition and purification with cold n-hexane except that desolvating 60～70 ℃ of backspins steamings, triplicate, at last 40～50 ℃ of vacuum drying to constant weight.
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