CN102172491B - Fluorine-contained surfactant and preparation method thereof - Google Patents
Fluorine-contained surfactant and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a fluorine-contained surfactant and a preparation method thereof. The fluorine-contained surfactant is characterized in that a fluorine-contained monomer and a non fluorine-contained monomer, such as acrylic ester are processed by an anion polymerization technology to obtain a segmented copolymer. Compared with the prior art, the fluorine-contained surfactant has a segmented structure, has the advantages of excellent surface activity, pure product, low polymerization temperature, high polymerization speed, wide application prospect and excellent efficacy in the field of leveling; and no active groups or catalysts are introduced in.
Description
Technical field
The invention belongs to chemical field, relate to a kind of fluorine-containing surfactant and preparation method thereof, be specifically related to a kind of block polymer being formed by the monomer of fluorochemical monomer and non-contain fluorine atoms.
Background technology
Fluorine-containing surfactant is a kind of fluoropolymer.Due to the special physics and chemistry character of fluorine, therefore than traditional surfactant, fluorine-containing surfactant has more advantage, for example: high surface, high heat-resistant stability and high chemical stability, not only hydrophobic but also hate oil of its fluorine-containing alkyl, so fluorine-containing surfactant is the highest one of surface-active in all surface activating agent up to now.The very low fluorine-containing surfactant of interpolation consumption just can greatly reduce the surface tension of water.Solving some can be low or surperficially have a greasy dirt due to surface, is difficult to wetting and spreading, the phenomenons such as the cissing that causes, shrinkage cavity, volcanic crater.The fluorine-containing surfactant adding in paint can make coating surface cover the fluorine carbon molecule of one deck hydrophobic oleophobic, and hydrone cannot permeate.Due to fluorocarbon chain also oleophobic in hydrophobic, so there is certain solvent resistance, improve the resistance to water of paint.Meanwhile, the general hydrophilic non-watertight property of paint film spot, and not grease proofness spot of hydrophobic paint film, can be in case various spot and added the paint film of fluorocarbon surfactant.Fluorocarbon surfactant has good temperature tolerance, even if baking temperature reaches 150 DEG C to 200 DEG C, still keeps stable, and plays a role.
This type of fluorine-containing surfactant, due to its unique character, can be widely used in industrial various aspects, for example: paint of coating, paper coating agent, cosmetic industry etc.The levelling that is specially adapted to microthin coating improves, as the photoresist paintability improvement being used in panel of LCD production process.
Liquid crystal display becomes the leading role of panel TV set and display gradually.For enhancing productivity, the glass substrate size of liquid crystal panel manufacturer processing is increasing, and liquid crystal panel production line is divided into different generations.The size of 1st generation liquid crystal glass base is only 300mm × 400mm, current main product be the 6th 8 generation of generation to the product, wherein the 6th generation liquid crystal glass base be of a size of 1,500mm × 1,800mm, and the 8th generation liquid crystal glass base size reach 2,200mm × 2,600mm.For the rule adjustment according to correct is by the luminous flux of colored filter, need on glass substrate, make tft array, this is that very complicated circuit multilayer is scribed engineering.Wherein mainly contain film (metal, dielectric or electro-conductive glass) and form, spray the operations such as photoresist, partly shielding effect exposure, development and etching, because need to repeatedly make different film patterns, therefore the coating performance of photoresist plays vital effect.The interpolation of surfactant can keep photoresist homogeneity, improve coating etc.Particularly, in the time that photoresist is coated on base material, on surface, can produce flakey texture, and by using surfactant, can suppress this scale spot, eliminate the defect (Mura) in coating process.
In recent years, for the research of fluorine-containing block polymer, research work both domestic and external concentrates on structural design, the synthetic method of fluoropolymer in a large number.In prior art, fluoropolymer is mainly to utilize free radical polymerisation process to implement.For example: Jean-Marc C. etc. utilizes radical polymerization, synthesized random copolymer (the Jean-Marc C. of trifluoroethyl methacrylate and a-fluoropropenes acid trichloro ethyl ester; Veronique M.; Bruno A.; Journal of Polymer Science:Part A:Polymer Chemistry, Vol.48,2154-2161 (2010)).But, there is the copolymer that the polymer of Narrow Molecular Weight Distribution and compound with regular structure prepared with respect to usual manner and demonstrate significantly different behavior and performances.Controlled free radical polymerization provides to have can expect and maximum control that the polymer of definite structure is synthetic.Recently, research has found to utilize active free radical polymerization to prepare the possible technique of various block copolymer.For example: active atomic transferring free-radical polymerization (ATRP) and reversible addition-fracture chain shift (RAFT) polymerization.Chinese Patent Application No. 200780049949.9 discloses employing ATRP (ATRP) and reversible addition-fracture chain shifts polymethylacrylic acid trifluoro ethyl ester and methacrylic acid diethylin ethyl ester block copolymer prepared by (RAFT) polymerization.ATRP method has advantages of that it is unique, but its maximum shortcoming is to contain metallic catalyst in final product, is difficult to remove, and product is impure.Fangping Yi utilizes RAFT polymerization to prepare fluorine-containing bi-block copolymer, and has studied its self-assembly property (FangpingYi; Sixun Zheng.; J.Phys.Chem.B 2009,113,1857-1868).Although RAFT polymerization has the features such as reaction condition gentleness, the RAFT reagent adding in polymerization process (sulfur-bearing thing) can remain in final polymer, is difficult to remove, and the performance of polymer is produced to certain impact.Meanwhile, RAFT reagent preparation process complexity, suitability for industrialized production difficulty is larger.It is many that active anionic polymerization has suitable monomers, and activated centre is stable, and polymerization speed is fast, and solvent range of choice is large, polymerization temperature wide ranges, and can carry out the advantages such as the design of different kinds of molecules structure is synthetic.Be used widely in industrial quarters, for example, Chinese invention patent application numbers 200810117321.4 discloses and has utilized organo-lithium compound in organic hydrocarbon solvent, use conjugated diolefin homopolymerization as anionic polymerization initiator or use conjugated diene and carry out copolymerization and prepare polymer with monovinylarene.
Therefore, a kind of novel block type fluorine-containing surfactant is provided, and can obtain the preparation method of pure polymerizate, the overall performance of fluorine-containing surfactant will be contributed to improve, enrich fluorine-containing surfactant kind, can be coating, ink etc., particularly photoresist provides the surface-active of function admirable.
Summary of the invention
The object of the invention is to provide a kind of have block structure and excellent surface-active fluorine-containing surfactant, has and is intended to be applied to photoresist field, solves the defect problem in photoresist film forming procedure.
For achieving the above object, the technical solution used in the present invention is:
A kind of fluorine-containing surfactant, is characterized in that this fluorine-containing surfactant is the block copolymer being obtained by the first fluorine-containing monomer and the second not fluorine-containing monomer polymerization of following general formula (I) expression;
Wherein, X is that hydrogen, fluorine, chlorine, bromine, iodine, cyano group or carbon number are 1～20 straight or branched fluoro-alkyl; Or the carbon number straight or branched alkyl that is 1～20; Replace or non-substituted phenyl, wherein, substituting group is that carbon number is 1～4 straight or branched alkyl, substituting group number is 1～2; X is preferably hydrogen, fluorine, chlorine, methyl or phenyl.
Y is that carbon number is 1～10 aliphatic group; Or the carbon number cyclic aliphatic group that is 6～10; Or the carbon number aromatic group that is 6～10; Y structure is preferably :-CH
2-,-CH
2cH
2-,-CH
2cH
2cH
2-,-C (CH
3)
2-,-CH
2cH
2cH
2cH
2-,-CH
2c (CH
3)
2-,-(CH
2)
2c (CH
3)
2-,-CH
2c (CH
3)
2-,-CH (CH
3) CH
2cH
2cH
2-,-(CH
2)
8cH
2-,
Rf group is that carbon number is 1～6 perfluoroalkyl or part fluoro-alkyl; Be preferably-CF of Rf group
3,-CF
2cF
3,-CF
2cF
2cF
3,-CF (CF
3)
2,-CF
2cF
2cF
2cF
3,-CF
2cF (CF
3)
2,-C (CF
3)
3,-(CF
2)
4cF
3,-(CF
2)
2cF (CF
3)
2,-CF
2c (CF
3)
3,-CF (CF
3) CF
2cF
2cF
3or-(CF
2)
5cF
3.
Described the second not fluorine-containing monomer is: vinyl ester, polystyrene compound or the acrylic amide of acrylic or methacrylic esters of gallic acid, aliphatic olefin propyl ester class, aliphatic acid.
Wherein, described acrylic or methacrylic esters of gallic acid is preferably methyl acrylate, acrylic acid ethyl ester, butyl acrylate cores, acrylic acid isobutyl, acrylic acid tertiary butyl ester, acrylic acid propyl diester, 2-EHA base, acrylic acid decyl ester, acrylic acid isodecyl ester, acrylic acid Lauryl Ester, stearyl acrylate base ester, acrylic acid iso stearyl ester, isobornyl acrylate, glycidyl acrylate base ester, phenyl acrylate, acrylic acid benzyl ester, acrylic acid 4-cyano-phenyl ester, acrylic acid dimethylamino ethyl ester, acrylic acid diethyl amino ethyl ester,
Or methyl methacrylate, methacrylic acid ethyl ester, methacrylic acid butyl ester, methacrylic acid isobutyl, methacrylic acid tertiary butyl ester, methacrylic acid propyl diester, methacrylic acid 2-ethylhexyl, methacrylic acid decyl ester, methacrylic acid isodecyl ester, methacrylic acid Lauryl Ester, methacrylic acid stearyl, methacrylic acid iso stearyl ester, IBOMA, GMA base ester, methacrylic acid phenylester, methacrylic acid benzyl ester, methacrylic acid 4-cyano-phenyl ester, dimethylaminoethyl acrylate methyl base ammonia ethyl ester, methacrylic acid diethyl amino ethyl ester,
Described aliphatic olefin propyl ester class is preferably allyl heptanoate, allyl octanoate, allyl acetate;
The vinyl ester of described aliphatic acid is preferably vinyl-acetic ester, vinyl propionate base ester, sad vinyl esters, laurate vinyl esters, vinyl stearate base ester;
Described polystyrene compound is preferably styrene or p-methylstyrene;
Described acrylic amide is preferably N methacrylamide or N hydroxymethyl acrylamide.
In fluorine-containing surfactant of the present invention, the percentage that the first monomer accounts for total polymer weight is 10%～90%, preferably 40%～60%; The percentage that the second monomer accounts for total polymer weight is 90%～10%, preferably 40%～60%.
The preparation method of fluorine-containing surfactant of the present invention obtains block copolymer by fluorine-containing first monomer of following general formula (I) expression and the second not fluorine-containing monomer by anion initiated polymerization:
Described anion initiated polymerization is for carrying out discontinuously, be specially: in high vacuum polyplant, add polymerization solvent, simultaneously or after one after the other adding initator to cause, add the first monomer polymerization, polymerization time is 0.5～15 hour, is preferably 1～3 hour, then adds the second monomer polymerization 0.5～3 hour, preferred polymeric 0.5～1 hour, after completing, polymerization adds terminator, reaction terminating, purifying polymer.
Described polymerization solvent is preferably cyclohexane, n-hexane or oxolane, more preferably oxolane, and solvent quality is 0.5: 1～5: 1 with the first monomer mass ratio, is preferably 1: 1～3: 1; Described initiators for polymerization is preferably (1 '-ethoxy ethoxy) propyl lithium or Ph
3cLi, consumption and the first monomer mole ratio are 1: 1～1.5, preferably 1: 1.2.Described polymeric reaction temperature is-100 DEG C～150 DEG C, is preferably-100 DEG C～110 DEG C, most preferably is-78 DEG C～30 DEG C.Described terminator is preferably water, methyl alcohol or isopropyl alcohol, and the mol ratio of terminator and initator is 0.1～1.1.The weight ratio that the first monomer and the second monomer are taken is 10～90: 90～10, and preferred weight ratio is 40～60: 60～40.
Beneficial effect of the present invention compared with the prior art: fluorine-containing surfactant of the present invention has block structure and excellent surface-active, product is pure, do not introduce active group or catalyst, and polymerization temperature is lower, polymerization speed is fast, the prospect that will be widely used, especially has very outstanding effectiveness in levelling field.Particularly be applied to photoresist field, solved the defect problem in photoresist film forming procedure.
The performance test methods of above-mentioned fluorine-containing surfactant: by common technique formulated positive photoresist, control the wherein content of fluorine-containing surfactant, and be coated with test.After base plate glass sheet is cleaned, dried, with 2000 revs/min of rotating speeds, the condition of 30 seconds whirl coating time, prepared photoresist is spin-coated on to glass baseplate surface with photoresist spinner, formation photoresist film carries out front baking 90 seconds on 100 DEG C of hot plates.Cooling rear observation is also tested thickness.
Foregoing description is also not used in restriction, but for explaining effect.Part below provides especially also mode by way of example to describe embodiments of the invention.Provide these embodiment as explanation of the invention effect, and do not mean that limitation of the invention.
Brief description of the drawings
Fig. 1 has shown gel permeation chromatography (GPC) figure of the fluorine-containing surfactant of preparing according to embodiment 1.Wherein a is the first block GPC figure, and b for continuing polymerization gained bi-block copolymer GPC figure on the first block basis.
Fig. 2 has shown the Painting effect figure of the photoresist that does not add the fluorine-containing surfactant described in embodiment 1.
Fig. 3 shows the Painting effect figure of the photoresist that has added the fluorine-containing surfactant described in embodiment 1.
Fig. 4 has shown the photoresist that has added the fluorine-containing surfactant described in embodiment 13, and surface-active contents is 1000ppm.
Fig. 5 shows the photoresist that has added the fluorine-containing surfactant described in embodiment 13, and surface-active contents is 1500ppm.
Fig. 6 shows the photoresist that has added the fluorine-containing surfactant described in embodiment 13, and surface-active contents is 2000ppm.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described:
Embodiment 1:
Taking ether as solvent, in high-vacuum installation, make 1 '-ethoxy ethoxy) propyl chloride and lithium metal generation Lithiation, preparation (1 '-ethoxy ethoxy) propyl lithium.
Polymerization all adopts high vacuum (< 10
-3pa) carry out with sealing anionic polymerisation experimental technique. in high vacuum polyplant, taking 100～150mL THF as polymer solvent, 1.0mL 0.5mol/L
3(1 '-ethoxy ethoxy) propyl lithium is initator, initator and C
3f
7cH
2cH
2cH
2oCOCH=CH
2(mol ratio 1: 1.2) polymerisation was rapidly cooled to-78 DEG C by liquid nitrogen/isopropanol bath after 1～3 hour, slowly added 5.0～15.0g methyl styrene thereupon, behind polymerase 10 .5～1 hour, added 0.02 gram of CH
3oH cessation reaction.Reacted polymer, under 60～70 DEG C of conditions, revolves and steams except desolventizing, carries out deposition and purification with n-hexane, in triplicate, is finally dried to constant weight 40～50 DEG C of vacuum drying ovens.Obtain required product, recording productive rate is 96%.Product through gel permeation chromatography (GPC) and proton nmr spectra and fluorine spectrum (
1h NMR,
19f NMR) detect the structure of its molecular weight, molecular weight distribution and copolymer, prove to have obtained target product, number-average molecular weight is 8780g/mol.
Embodiment 2～4:
Except the fluorochemical monomer kind changing in embodiment 1, initator, solvent, the second monomer, polymerization temperature are equal to described in embodiment 1 identical.Wherein the fluorochemical monomer that uses respectively is: (CF
3)
2cF (CF
2)
2c (CH
3)
2oCOCH=CH
2, (CF
3)
3cCF
2cH
2c (CH
3)
2oCOCH=CH
2, CF
3cF
2cF
2(CF
3) CFCH
2cH
2cH
2cH
2oCOCH=CH
2.Obtaining polymer number-average molecular weight is 9000～10000.
Embodiment 5～8:
Except the fluorochemical monomer kind and the second monomer that change in embodiment 1, initator, solvent, polymerization temperature are equal to described in embodiment 1 identical.Wherein use the second monomer for acrylic acid 4-cyano-phenyl ester, the first fluorine-containing monomer is respectively:
obtaining polymer number-average molecular weight is 1000～100000.
Embodiment 9:
Taking ether as solvent, in high-vacuum installation, make Ph
3cCl and lithium metal generation Lithiation, preparation Ph
3cLi.
Polymerization all adopts high vacuum (< 10
-3pa) carry out with sealing anionic polymerisation experimental technique.In high vacuum polyplant, taking 100～150mL oxolane (THF) as polymer solvent, 1.0mL 0.5mol/L
3ph
3cLi is initator, initator and (CF
3)
3cCH
2cH
2cH
2oCOCH=CH
2after (mol ratio 1: 1.2) reaction, be cooled to-78 DEG C by liquid nitrogen/isopropanol bath rapidly, slowly add 5.0～15.0g styrene thereupon, after polymerase 10 .5～1h, add 0.01 gram of deionized water cessation reaction.Reacted polymer, under 60～70 DEG C of conditions, revolves and steams except desolventizing, carries out deposition and purification with n-hexane, in triplicate, is finally dried to constant weight 40～50 DEG C of vacuum drying ovens.Obtain required product, recording productive rate is 90%.Product through gel permeation chromatography (GPC) and proton nmr spectra and fluorine spectrum (
1h NMR,
19f NMR) detect the structure of its molecular weight, molecular weight distribution and copolymer, prove to have obtained target product.Obtaining polymer number-average molecular weight is 93520g/mol.
Embodiment 10～15:
Except the second monomeric species changing in embodiment 9, initator, solvent, fluorochemical monomer, polymerization temperature are equal to described in embodiment 9 identical.Wherein use the second monomer respectively to be: laurate vinyl esters, p-methylstyrene, isobutyl methacrylate, N methacrylamide, acrylic acid dimethylamino ethyl ester, methacrylic acid diethyl amino ethyl ester.Obtaining polymer number-average molecular weight is 10000～100000.
Embodiment 16～18:
Except the fluorochemical monomer kind and the second monomer that change in embodiment 9, be cooled to outside-100 DEG C by liquid nitrogen/isopropanol bath, initator, solvent, polymerization temperature are equal to described in embodiment 9 identical.Wherein use the second monomer for stearyl acrylate base ester, the first fluorine-containing monomer respectively is:
obtaining polymer number-average molecular weight is 1000～100000.
Embodiment 19:
By common technique formulated positive photoresist, wherein (number-average molecular weight is respectively 2100,4248 to phenolic resins, weight ratio is 1.5: 1), emulsion 2,3,4, carboxylate, the solvent 1-Methoxy-2-propyl acetate content of 4 '-tetrahydroxybenzophenone and 1,2-naphthoquinones, two nitrine-5-sulfonic acid chloride are respectively 20%, 3%, 77%.Fluorine-containing surfactant described in interpolation embodiment 1, content is respectively 0ppm and 4500ppm and is coated with test.After base plate glass sheet is cleaned, dried, with 2000 revs/min of rotating speeds, the condition of 30 seconds whirl coating time, prepared photoresist is spin-coated on to glass baseplate surface with photoresist spinner, formation photoresist film carries out front baking 90 seconds on 100 DEG C of hot plates.Cooling rear observation is also tested thickness.Shown in result accompanying drawing 3, added after fluorine-containing surfactant, than not adding surfactant (referring to accompanying drawing 2), photoresist coating performance obviously improves, and defect (Mura) disappears.
Embodiment 20:
By common technique formulated positive photoresist, wherein (number-average molecular weight is respectively 2100,4248 to phenolic resins, weight ratio is 1.5: 1), emulsion 2,3,4, carboxylate, the solvent 1-Methoxy-2-propyl acetate content of 4 '-tetrahydroxybenzophenone and 1,2-naphthoquinones, two nitrine-5-sulfonic acid chloride are respectively 20%, 3%, 77%.Surfactant described in interpolation embodiment 3, content is 4500ppm and is coated with test.After base plate glass sheet is cleaned, dried, with 5000 revs/min of rotating speeds, the condition of 20 seconds whirl coating time, prepared photoresist is spin-coated on to glass baseplate surface with photoresist spinner, formation photoresist film carries out front baking 90 seconds on 100 DEG C of hot plates.Cooling rear observation is also tested thickness.
Embodiment 21:
By common technique formulated positive photoresist, wherein (number-average molecular weight is respectively 1200,3899 to phenolic resins, weight ratio is 2: 1), emulsion 2,3,4, carboxylate, the solvent 1-Methoxy-2-propyl acetate content of 4 '-tetrahydroxybenzophenone and 1,2-naphthoquinones, two nitrine-5-sulfonic acid chloride are respectively 25%, 4.5%, 70.5%.Control the wherein content of fluorine-containing surfactant, and be coated with test, fluorine-containing surfactant used is described in embodiment 13.By Wafer Cleaning, dry after, with 4000 revs/min of rotating speeds, the condition of 25 seconds whirl coating time, prepared photoresist is spin-coated on to silicon chip surface with photoresist spinner, formation photoresist film carries out front baking 90 seconds on 110 DEG C of hot plates.Cooling rear observation is also tested thickness.As shown in accompanying drawing 4～6, its fluorosurfactant is respectively 1000ppm (accompanying drawing 4), 1500ppm (accompanying drawing 5), 2000ppm (accompanying drawing 6).In the time that fluorosurfactant is increased to 2000ppm, filming performance obviously improves, and defect (Mura) disappears.
Embodiment 22～24:
Except the fluorine-containing surfactant kind changing in embodiment 21, photoresist resin, emulsion, solvent, coating method are equal to described in embodiment 11 identical.The wherein surfactant that uses, respectively is described in embodiment 7,9,18.
Claims (10)
1. a preparation method for fluorine-containing surfactant, is characterized in that this fluorine-containing surfactant is to be represented by following general formula (I)
The first fluorine-containing monomer and the block copolymer that obtains by anion initiated polymerization of the second not fluorine-containing monomer;
Wherein, X is that hydrogen, fluorine, chlorine, bromine, iodine, cyano group or carbon number are 1～20 straight or branched fluoro-alkyl; Or the carbon number straight or branched alkyl that is 1～20; Replace or non-substituted phenyl, wherein, substituting group is that carbon number is 1～4 straight or branched alkyl, substituting group number is 1～2;
Y is that carbon number is 1～10 aliphatic group; Or the carbon number cyclic aliphatic group that is 6～10; Or the carbon number aromatic group that is 6～10;
Rf group is that carbon number is 1～6 perfluoroalkyl or part fluoro-alkyl;
Described the second not fluorine-containing monomer is: vinyl ester, polystyrene compound or the acrylic amide of acrylic or methacrylic esters of gallic acid, aliphatic olefin propyl ester class, aliphatic acid;
Described anion initiated polymerization, for carrying out discontinuously, is specially: in high vacuum polyplant, add polymerization solvent, simultaneously or after one after the other adding initator to cause, add the first monomer polymerization, polymerization time is 0.5～15 hour; Add again the second monomer polymerization 0.5～3 hour, after polymerization completes, add terminator, reaction terminating, purifying polymer; Described polymerization solvent is oxolane; Described initiators for polymerization is (1'-ethoxy ethoxy) propyl lithium or Ph
3cLi, consumption and the first monomer mole ratio are 1:1～1.5.
2. the preparation method of fluorine-containing surfactant as claimed in claim 1, is characterized in that X is hydrogen, fluorine, chlorine, methyl or phenyl.
3. the preparation method of fluorine-containing surfactant as claimed in claim 1, is characterized in that described Y structure is :-CH
2-,-CH
2cH
2-,-CH
2cH
2cH
2-,-C (CH
3)
2-,-CH
2cH
2cH
2cH
2-,-CH
2c (CH
3)
2-,-(CH
2)
2c (CH
3)
2-,-CH
2c (CH
3)
2-,-CH (CH
3) CH
2cH
2cH
2-,-(CH
2)
8cH
2-,
,
,
or
.
4. the preparation method of fluorine-containing surfactant as claimed in claim 1, described Rf group is-CF
3,-CF
2cF
3,-CF
2cF
2cF
3,-CF (CF
3)
2,-CF
2cF
2cF
2cF
3,-CF
2cF (CF
3)
2,-C (CF
3)
3,-(CF
2)
4cF
3,-(CF
2)
2cF (CF
3)
2,-CF
2c (CF
3)
3,-CF (CF
3) CF
2cF
2cF
3or-(CF
2)
5cF
3.
5. the preparation method of fluorine-containing surfactant as claimed in claim 1, it is characterized in that described acrylic or methacrylic esters of gallic acid is methyl acrylate, acrylic acid ethyl ester, butyl acrylate cores, acrylic acid isobutyl, acrylic acid tertiary butyl ester, acrylic acid propyl diester, 2-EHA base, acrylic acid decyl ester, acrylic acid isodecyl ester, acrylic acid Lauryl Ester, stearyl acrylate base ester, acrylic acid iso stearyl ester, isobornyl acrylate, glycidyl acrylate base ester, phenyl acrylate, acrylic acid benzyl ester, acrylic acid 4-cyano-phenyl ester, acrylic acid dimethylamino ethyl ester, acrylic acid diethyl amino ethyl ester,
Or methyl methacrylate, methacrylic acid ethyl ester, methacrylic acid butyl ester, methacrylic acid isobutyl, methacrylic acid tertiary butyl ester, methacrylic acid propyl diester, methacrylic acid 2-ethylhexyl, methacrylic acid decyl ester, methacrylic acid isodecyl ester, methacrylic acid Lauryl Ester, methacrylic acid stearyl, methacrylic acid iso stearyl ester, IBOMA, GMA base ester, methacrylic acid phenylester, methacrylic acid benzyl ester, methacrylic acid 4-cyano-phenyl ester, dimethylaminoethyl acrylate methyl base ammonia ethyl ester, methacrylic acid diethyl amino ethyl ester,
Described aliphatic olefin propyl ester class is allyl heptanoate, allyl octanoate, allyl acetate;
The vinyl ester of described aliphatic acid is vinyl-acetic ester, vinyl propionate base ester, sad vinyl esters, laurate vinyl esters, vinyl stearate base ester;
Described polystyrene compound is styrene or p-methylstyrene;
Described acrylic amide is N methacrylamide or N hydroxymethyl acrylamide.
6. the preparation method of fluorine-containing surfactant as claimed in claim 1, is characterized in that the percentage that the first monomer accounts for total polymer weight is 10%～90%; The percentage that the second monomer accounts for total polymer weight is 90%～10%.
7. the preparation method of fluorine-containing surfactant as claimed in claim 6, is characterized in that the percentage that the first monomer accounts for total polymer weight is 40%～60%; The percentage that the second monomer accounts for total polymer weight is 40%～60%.
8. the preparation method of fluorine-containing surfactant according to claim 1, wherein said initiators for polymerization consumption and the first monomer mole ratio are 1:1.2.
9. the preparation method of fluorine-containing surfactant according to claim 1, is characterized in that described terminator is water, methyl alcohol or isopropyl alcohol, and the mol ratio of terminator and initator is 0.1～1.1.
10. the preparation method of fluorine-containing surfactant according to claim 1, is characterized in that described polymerization time is 1～3 hour.
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Families Citing this family (26)
| Publication number | Priority date | Publication date | Assignee | Title |
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| EP3101043B1 (en) * | 2013-12-06 | 2021-01-27 | LG Chem, Ltd. | Block copolymer |
| JP6402867B2 (en) | 2013-12-06 | 2018-10-10 | エルジー・ケム・リミテッド | Block copolymer |
| WO2015084131A1 (en) | 2013-12-06 | 2015-06-11 | 주식회사 엘지화학 | Block copolymer |
| JP6419820B2 (en) * | 2013-12-06 | 2018-11-07 | エルジー・ケム・リミテッド | Block copolymer |
| EP3078690B1 (en) * | 2013-12-06 | 2021-01-27 | LG Chem, Ltd. | Block copolymer |
| US10227438B2 (en) | 2013-12-06 | 2019-03-12 | Lg Chem, Ltd. | Block copolymer |
| WO2015084123A1 (en) | 2013-12-06 | 2015-06-11 | 주식회사 엘지화학 | Block copolymer |
| JP6496318B2 (en) | 2013-12-06 | 2019-04-03 | エルジー・ケム・リミテッド | Block copolymer |
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| JP6538159B2 (en) | 2014-09-30 | 2019-07-03 | エルジー・ケム・リミテッド | Block copolymer |
| US10287430B2 (en) | 2014-09-30 | 2019-05-14 | Lg Chem, Ltd. | Method of manufacturing patterned substrate |
| US10310378B2 (en) | 2014-09-30 | 2019-06-04 | Lg Chem, Ltd. | Block copolymer |
| CN106758234B (en) * | 2017-01-11 | 2019-03-29 | 东华大学 | A kind of hydrophilic preparation method for refusing oily automatically cleaning cotton fabric |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2001011107A (en) * | 1999-06-29 | 2001-01-16 | Hitachi Chem Co Ltd | Resin paste composition and semiconductor device produced by using the composition |
| CN1670051A (en) * | 2004-03-17 | 2005-09-21 | 中国科学院成都有机化学有限公司 | Fluorine-containing polyurethane emulsion and method for preparing same |
| CN1300192C (en) * | 2004-09-17 | 2007-02-14 | 浙江大学 | Preparation of water dispersed fine emulsion of fluorine acrelate copolymer for anti-oil and anti-water agent |
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