CN103694429B - fluorine-containing block copolymer and preparation method and application thereof - Google Patents
fluorine-containing block copolymer and preparation method and application thereof Download PDFInfo
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- CN103694429B CN103694429B CN201410016615.3A CN201410016615A CN103694429B CN 103694429 B CN103694429 B CN 103694429B CN 201410016615 A CN201410016615 A CN 201410016615A CN 103694429 B CN103694429 B CN 103694429B
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Abstract
The invention relates to a fluorine-containing block copolymer and a preparation method and application thereof. The weight-average molecular weight of the polymer is 5,000-100,000, and the polymer is prepared by polymerizing 15-65wt% of monomer A, 10-80wt% of monomer B, 0.5-15wt% of monomer C and 0.5-10wt% of monomer D in an atom transfer radical polymerization (ATRP) way. Compared with the traditional fluorine-containing random copolymer obtained by common free radical polymerization, the fluorine-containing block copolymer with fewer than 8 carbon atom in perfluoroalkyl group and synthesized in an ATRP way integrates the characteristics of oil repellency, antifouling property, decontamination and good solubility when used as an antifouling agent and a decontamination agent; moreover, under the condition of the same dosage of perfluoroalkyl group, better oil repellency can be obtained.
Description
Technical field
The present invention relates to a kind of fluorinated block copolymer and its preparation method and application.
Background technology
As oil repellent, soil resistances such as imparting fabric fibres, and it is easy to remove attachment on fiber by washing etc.
The antifouling agent of spot it is known that this kind of antifouling agent generally by have the acrylic ester monomer of perfluoroalkyl with containing hydrophilic
Group compound copolymerization obtains.
But, mostly more than 8, this year is from the impact to environment for the carbon number of Polyfluoroalkyl being used for these processing agents
Angle considers, the carbon number with perfluoroalkyl in the compound of perfluoroalkyl is preferably lower than 8.
When the carbon number using perfluoroalkyl is less than 8 metha crylic comonomer, antifouling agent occurs refusing oil
The insufficient problem of performance, or the oil repellency fully soil release performance problem low with dissolubility.
Content of the invention
The technical problem to be solved is to provide a kind of excellent oil repellent of imparting fibre, soil resistance, go
Dirt, and the carbon number of perfluoroalkyl is less than 8 fluorinated block copolymer.
Another technical problem to be solved by this invention is to provide a kind of preparation method of above-mentioned fluorinated block copolymer.
Another technical problem to be solved by this invention is to provide a kind of antifouling agent.
Another technical problem to be solved by this invention is to provide a kind of stain-proofing agent composition.
For solving above technical problem, the present invention adopts the following technical scheme that:
A kind of fluorinated block copolymer, is polymerized and obtains through ATRP (atrp) mode by monomer, and this is altogether
The weight average molecular weight of polymers is 5000～100000, with weight, described monomer by 15%～65 monomer a, 10%
～80% monomer b, 0.5%～15% monomer c, 0.5%～10% monomer d composition, wherein,
The general structure of monomer a is ch2=c(x)-coo-ch2ch2- rf, in formula: x is hydrogen, chlorine, fluorine or methyl；Rf is complete
Fluorine hexyl or perfluoro butyl；
The general structure of monomer b is ch2=c(r1)-coo-(c2h4o)a-(c3h6o)b-(c4h8o)c-r2, in formula: r1For hydrogen
Or methyl；A is integer between 0～50, b is integer between 0～20, c is integer between 0～20；r2For hydroxyl or first
Epoxide；
The general structure of monomer c is ch2=c(y)-cor3-(ch2)d- oh, in formula: y is hydrogen or methyl；r3For oxygen or amido；
D is the integer between 1～6；
The general structure that monomer d is is ch2=c(ch3)-coo-ch2-r4, in formula: r4For tertiary amine, tertiary ammonium salt or quaternary ammonium salt.
Specifically, described monomer a is ch2=c(h)-coo-ch2ch2-cf2cf2cf2cf2cf2cf3、ch2=c(ch3)-
coo-ch2ch2-cf2cf2cf2cf2cf2cf3、ch2=c(f)-coo-ch2ch2-cf2cf2cf2cf2cf2cf3、ch2=c(cl)-coo-
ch2ch2-cf2cf2cf2cf2cf2cf3、ch2=c(h)-coo-ch2ch2-cf2cf2cf2cf3、ch2=c(ch3)-coo-ch2ch2-
cf2cf2cf2cf3、ch2=c(f)-coo-ch2ch2-cf2cf2cf2cf3、ch2=c(cl)-coo-ch2ch2-cf2cf2cf2cf3In
One or more of combination.
More specifically, described monomer a is perfluoro hexyl ethylmethyl acrylate or perfluoro hexyl ethyl alpha-chloro third
Olefin(e) acid ester.
Specifically, described b is ch2=c(ch3)-coo-(c2h4o)5-oh、ch2=c(ch3)-coo-(c2h4o)9-oh、ch2
=c(ch3)-coo-(c2h4o)20-oh、ch2=c(ch3)-coo-(c2h4o)5-o-ch3、ch2=c(ch3)-coo-(c2h4o)9-o-
ch3、ch2=c(ch3)-coo-(c2h4o)20-o-ch3、ch2=c(ch3)-coo-(c2h4o)15-(c3h6o)3–oh、ch2=c(ch3)-
coo-(c2h4o)20-(c4h8o)5-oh、ch2=c(ch3)-coo-(c2h4o)15-(c3h6o)3-o-ch3、ch2=c(ch3)-coo-
(c2h4o)20-(c4h8o)5-o-ch3One or more of combination.
Specifically, described c is hydroxyethyl methacrylate, hydroxy propyl methacrylate, methacrylate, hydroxyl
The combination of one or more of Methacrylamide.
Specifically, described monomer d is methacrylic acid n, n- dimethylaminoethyl and its acetate, methacrylic acid n,
The combination of one or more of n- lignocaine ethyl ester and its acetate, 2- MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride.
Specifically, described copolymer is made by the steps and obtains: will be molten for any one monomer in monomer a, b, c, d
Solution, in organic solvent, adds initiator, the gold of ATRP of ATRP in system
Metal catalyst, the metal catalyst complex of ATRP, after being passed through nitrogen displacement, sealing system, 25～110
It is polymerized under the conditions of DEG C, when monomer conversion reaches more than 95%, in importing monomer a, b, c, d in system, three kinds of residue appoints
Two kinds of monomers of meaning, repeat the above steps, when monomer conversion reaches more than 95%, then import a kind of remaining monomer to system,
When monomer conversion is more than 99%, it is passed through air, terminating reaction, removes described metallic catalyst, then add in system
Acid desalted water, stirs, and obtains final product described fluorinated block copolymer.
A kind of preparation method of above-mentioned fluorinated block copolymer, comprise the steps: by monomer a, b, c, d any one
Monomer is dissolved in organic solvent, adds the initiator of ATRP, atom transferred free radical to gather in system
The metallic catalyst of conjunction, the metal catalyst complex of ATRP, after being passed through nitrogen displacement, sealing system,
It is polymerized under the conditions of 25～110 DEG C, when monomer conversion reaches more than 95%, import in system remaining three in monomer a, b, c, d
Any two kinds of monomers planted, repeat the above steps, when monomer conversion reaches more than 95%, then import remaining one to system
Plant monomer, when monomer conversion is more than 99%, is passed through air, terminating reaction, by reactant liquor through alumina filled post, removes
To in system, after described metallic catalyst, add the desalted water of acidity, stir, obtain final product described fluorine-containing block copolymerization
Thing.
Preferably, described organic solvent is toluene, dimethylbenzene, the mixed solvent (90/ of benzotrifluoride, methyl alcohol and water
10v/v), methyl ethyl ketone, ethyl acetate, dipropylene glycol monomethyl ether, DPG, tripropylene glycol, 1,4- dioxane (two evils
Alkane), methyl phenyl ethers anisole, dmf (n, n- dimethylformamide), dmso (dimethyl sulfoxide) or isopropanol.
Preferably, the initiator of atrp is alkyl halide, benzylic halides, alpha-halogen ester, α-halogenatedketone, alpha-halogen nitrile.
It is highly preferred that the initiator of described atrp is alpha-bromo ethyl acetate.
Preferably, the metallic catalyst of atrp is copper and mantoquita.
It is highly preferred that the metallic catalyst of atrp is stannous chloride, copper chloride, cuprous bromide, copper bromide.
Preferably, the metal catalyst complex of atrp is the derivative of pyridine structure contained unit, the construction unit containing tertiary amine
Derivative.
It is highly preferred that the metal catalyst complex of atrp is bipyridyl or n, n, n', n, ' n''- pentamethyl diethylidene three
Amine.
A kind of fluorinated block copolymer is used as the purposes of antifouling agent.
A kind of stain-proofing agent composition includes above-mentioned fluorinated block copolymer and aqueous medium.
Due to the enforcement of above technical scheme, the present invention compared with prior art has the advantage that
The carbon number of the perfluoroalkyl that the present invention is synthesized by way of atrp be less than 8 fluorinated block copolymer with led in the past
Cross general radical polymerization obtain fluorine-containing random copolymer compare, as antifouling, detergent uses when, had both and refused oil
The feature of property, soil resistance, soil release performance and good dissolubility, and under the conditions of identical perfluoroalkyl consumption, can obtain
More excellent oil repellent.
Specific embodiment
Detergency test
Remove oil dirt according to being designed for measurement fabric in common Household laundry processes in aatcc130-1981(
The ability of stain) in description, described copolymer material is tested as detergent.In this approach, negative by applying
Lotus makes a certain amount of spot enter in fabric, thus obtaining the oily spot in test sample, stained fabrics is washed, and
The spot of residual is chosen as by 1 to 5 grades using standard stain release duplicate.Numerical value 5 represents maximally effective decontamination property and numerical value 1
Represent worst.Median gives the numerical value between 1 and 5.
Described test is specific as follows to be carried out, and places 5 specifically oil dyes in the middle of substantially close to test fabric sample
Dirty reagent.Subsequently a square glassine paper is placed on above fabric, covers spot, above described glassine paper, compress 2.3kg's
Weight, after 60 seconds, removes weight and glassine paper, in standard washer, adopts 140g's at a temperature of 41 DEG C
" tide " board is washed adjustment and is washed test sample 15 to 60 minutes, using test sample ballast (weighing 1.8kg altogether) 12 points of ballast
Clock, the sample subsequently being filled whole washing machine and ballast are placed in dryer and at maximum air exit temp is 75 DEG C
It is dried 45 minutes, then reference standard grade is judged (table 1) to the test sample being dried as mentioned above.
Table 1
| Decision level | Criterion |
| 1.0 | Substantially remain spot |
| 2.0 | Quite remain spot |
| 3.0 | Remain spot a little |
| 4.0 | Spot is inconspicuous |
| 5.0 | Non- residual stains |
Anti- oil test
Tested by aatcc-118 method.The hydrocarbon liquids homologue being reduced successively using 8 kinds of surface tension as standard,
Respectively various standard solutions (being shown in Table 2) are dripped on the surface of the fabric with dropper, by numerical value minimum test liquid (classification of waterproof 1
Level) start, it is separated by each described liquid (diameter of about 5mm or the body of 0.05ml at least on the position of 5mm at three
Long-pending).Observe described drop 30 seconds, if at the end of this stage, two during three dropping liquids drip is in still spherical without along liquid
Drip and absorbed, then the drop of the higher numerical value of the next one is dripped three and drop on adjacent position and equally observation 30 seconds.Proceed
Operation until one of test liquid three dropping liquids drip in two can not keep spherical to hemispherical, occur wetting or inhale
Receive.Generally have 5 or greater degree treated fabric be considered good to excellent；Have 1 or the fabric of greater degree can
Use in some applications.
Table 2
Embodiment 1
Methoxy poly (ethylene glycol) (eo10mol) monomethacrylates 100g, dipropyl is loaded in the four-hole boiling flask of 500ml
Glycol monomethyl ether 100g, alpha-bromo ethyl acetate 0.5g, n, n, n', n, ' n''- five methyl diethylentriamine 1.0g, protobromide
Copper 0.8g, is passed through nitrogen displacement, band oxygen content is down to below 100ppm, is warming up to 80 DEG C, after reacting 6 hours, by gas phase color
Spectrum detection conversion ratio is more than 98%, then injection 10g hydroxyethyl methacrylate, 10g methacrylic acid n, n- diformazan ammonia in system
Base ethyl ester, after reacting 3 hours, is more than 98% by gas chromatographic detection conversion ratio, then injects 100g perfluoro hexyl second in system
Methyl acrylate (6fma), after reacting 20 hours, is more than 99% by gas chromatographic detection conversion ratio, is passed through air, fall
Temperature, terminating reaction, product, through alumina filled post, removes metallic catalyst.Follow the tracks of molecular weight by gel permeation chromatography to increase
Long situation and molecular weight distribution, confirmation product is block polymer, and weight average molecular weight is 4.5 ten thousand (polystyrene conversion), finally
To in system, addition acetic acid adjusts the desalted water that ph is 4, stirs, and forms fluorinated block copolymer solution, solids content
For 20%.
Embodiment 2～6
According to the monomer composition shown in table and proportioning, repeat step same as Example 1, finally give 20% solid
The solution of content, copolymer composition is as shown in table 3.
Table 3
Comparative example 1
Methoxy poly (ethylene glycol) (eo10mol) monomethacrylates 100g, 10g are loaded in the four-hole boiling flask of 500ml
Hydroxyethyl methacrylate, 10g methacrylic acid n, n- dimethylaminoethyl, 100g perfluoro hexyl ethylmethyl acrylate
(6fma), dipropylene glycol monomethyl ether 100g, 2g azodiisobutyronitrile, is passed through nitrogen displacement, is warming up to 80 DEG C, reacts 20 hours
Afterwards, it is more than 98% by gas chromatographic detection conversion ratio, lower the temperature, terminating reaction.Follow the tracks of molecular weight by gel permeation chromatography to increase
Situation and molecular weight distribution, confirmation product is block polymer, and weight average molecular weight is 2.8 ten thousand (polystyrene conversion), the most backward
In system, addition acetic acid adjusts the desalted water that ph is 4, stirs, and forms fluorine-containing random copolymer solution, and solids content is
20%.
Comparative example 2～6
According to the monomer composition shown in table and proportioning, repeat and comparative example 1 identical step, finally give 20% solid
The solution of content, copolymer composition is as shown in table 3.
Test example 1
The modulation of working process liquid:
30 parts of the fluorinated block copolymer solution obtaining in embodiment 1；
10 parts of blocked isocyanate cation emulsion (mdi class blocked isocyanate)；
60 parts of running water.
100% cotton drill is immersed in and operates as described above in the treatment fluid obtaining, remove unnecessary treatment fluid with roll,
Its upper liquid rate is made to be 60wt%.By this cloth under the conditions of 170 DEG C, it is dried 90 seconds, thus completes detergent-treatment.These cloth are surveyed
Determine soil release performance and oil repellent, result is as shown in table 4.
And, in order to evaluate washing resistance, on the basis of aatcc method, it is 40 DEG C in water temperature, every time wash time is 12
Minute, and carry out roller drying, circulate as one.Measure soil release performance and refuse to the processed cloth after this circulation is repeated
Oiliness.Result is as shown in table 4.
Embodiment 2～6 and comparative example 1～6
Fluorinated block copolymer solution is replaced with the material obtaining in embodiment 2～6 and comparative example 1～6 respectively, removes
Outside this, according to test example 1 identical step modulation treatment liquid, carry out cloth process, measure soil release performance and oil repellent.Result is such as
Shown in table 4.
Table 4
Note: in table, digital a～numeral b represents the performance in the middle of a and b；Hl10, hl20 represent respectively washing 10 times after, 20
After secondary.
Above the present invention is described in detail, its object is to allow the personage being familiar with this art will appreciate that this
The content of invention is simultaneously carried out, and can not be limited the scope of the invention with this, all Spirit Essence institutes according to the present invention
The equivalence changes made or modification, all should cover within the scope of the present invention.
Claims (8)
1. a kind of fluorinated block copolymer it is characterised in that: be polymerized through ATRP mode and obtained by monomer,
The weight average molecular weight of this copolymer is 5000 ~ 100000, with weight, described monomer by 15% ~ 65% monomer a,
10% ~ 80% monomer b, 0.5% ~ 15% monomer c, the monomer d composition of 0.5 % ~ 10%, wherein,
The general structure of monomer a is ch2=c(x)-coo-ch2ch2- rf, in formula: x is hydrogen, chlorine, fluorine or methyl；Rf is that perfluor is own
Base or perfluoro butyl；
The general structure of monomer b is ch2=c(r1)-coo-(c2h4o)a-(c3h6o)b-(c4h8o)c-r2, in formula: r1For hydrogen or first
Base；A be 0 ~ 50 between integer, b be 0 ~ 20 between integer, c be 0 ~ 20 between integer；r2For hydrogen or methyl；
The general structure of monomer c is ch2=c(y)-cor3-(ch2)d- oh, in formula: y is hydrogen or methyl；r3For oxygen or amido；D is 1
Integer between ~ 6；
Described monomer d is methacrylic acid n, n- dimethylaminoethyl and its acetate, methacrylic acid n, n- lignocaine
The combination of one or more of ethyl ester and its acetate, 2- MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride；Described copolymerization
Thing is made by the steps and obtains: monomer b is dissolved in organic solvent, adds ATRP in system
Initiator, the metallic catalyst of ATRP, the metal catalyst complex of ATRP, lead to
After entering nitrogen displacement, sealing system, is polymerized, under the conditions of 25 ~ 110 ° of c when monomer conversion reaches more than 95%, in system
Import monomer c and monomer d, repeat the above steps, when monomer conversion reaches more than 95%, then import monomer a to system, treat
When monomer conversion is more than 99%, it is passed through air, terminating reaction, removes described metallic catalyst, in system, then add acid
Property desalted water, stir, obtain final product described fluorinated block copolymer.
2. fluorinated block copolymer according to claim 1 it is characterised in that: described monomer a be ch2=c(h)-coo-
ch2ch2-cf2cf2cf2cf2cf2cf3、ch2=c(ch3)-coo-ch2ch2-cf2cf2cf2cf2cf2cf3、ch2=c(f)-coo-
ch2ch2-cf2cf2cf2cf2cf2cf3、ch2=c(cl)-coo-ch2ch2-cf2cf2cf2cf2cf2cf3、ch2=c(h)-coo-
ch2ch2-cf2cf2cf2cf3、ch2=c(ch3)-coo-ch2ch2-cf2cf2cf2cf3、ch2=c(f)-coo-ch2ch2-
cf2cf2cf2cf3、ch2=c(cl)-coo-ch2ch2-cf2cf2cf2cf3One or more of combination.
3. fluorinated block copolymer according to claim 2 it is characterised in that: described monomer a be perfluoro hexyl ethyl
Methacrylate or perfluoro hexyl ethyl α-chloro-acrylicacid ester.
4. fluorinated block copolymer according to claim 1 it is characterised in that: described monomer b be ch2=c(ch3)-
coo-(c2h4o)5-h 、ch2=c(ch3)-coo-(c2h4o)9-h 、ch2=c(ch3)-coo-(c2h4o)20-h 、ch2=c(ch3)-
coo-(c2h4o)5-ch3、ch2=c(ch3)-coo-(c2h4o)9-ch3、ch2=c(ch3)-coo-(c2h4o)20-ch3、ch2=c
(ch3)-coo-(c2h4o)15- (c3h6o)3–h、ch2=c(ch3)-coo-(c2h4o)20- (c4h8o)5-h、ch2=c(ch3)-
coo-(c2h4o)15- (c3h6o)3-ch3、ch2=c(ch3)-coo-(c2h4o)20- (c4h8o)5-ch3One or more of
Combination.
5. fluorinated block copolymer according to claim 1 it is characterised in that: described monomer c be hydroxyethyl methacrylate
The combination of one or more of ethyl ester, hydroxy propyl methacrylate, methacrylate, NMA.
6. a kind of preparation method of the fluorinated block copolymer as any one of claim 1 to 5 it is characterised in that: bag
Include following steps: monomer b is dissolved in organic solvent, adds the initiator, former of ATRP in system
The metallic catalyst of sub- transferring free-radical polymerization, the metal catalyst complex of ATRP, are passed through nitrogen displacement
Afterwards, sealing system, is polymerized under the conditions of 25 ~ 110 ° of c, when monomer conversion reaches more than 95%, imports monomer c in system
With monomer d, repeat the above steps, when monomer conversion reaches more than 95%, then import monomer a to system, treat monomer conversion
During more than 99%, it is passed through air, terminating reaction, removes described metallic catalyst, in system, then add the desalination of acidity
Water, stirs, and obtains final product described fluorinated block copolymer.
7. the fluorinated block copolymer any one of claim 1 to 5 is used as the purposes of antifouling agent.
8. a kind of stain-proofing agent composition it is characterised in that: it includes fluorine-containing embedding any one of claim 1 to 5
Section copolymer and aqueous medium.
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| CN1324877A (en) * | 2001-07-10 | 2001-12-05 | 华东理工大学 | Fluoroacrylic ester block polymer and its prpen. |
| CN102634980A (en) * | 2012-04-19 | 2012-08-15 | 常州大学 | Fluorine-containing waterproofing agent for textiles and method for preparing same |
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| WO2008093567A1 (en) * | 2007-02-02 | 2008-08-07 | Daikin Industries, Ltd. | Fluorine-containing copolymer having excellent washing resistance and soil release agent |
| CN103748126A (en) * | 2011-08-24 | 2014-04-23 | 旭硝子株式会社 | Fluorine-containing block copolymer, method for producing same, and surface treatment agent |
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| CN1324877A (en) * | 2001-07-10 | 2001-12-05 | 华东理工大学 | Fluoroacrylic ester block polymer and its prpen. |
| CN102634980A (en) * | 2012-04-19 | 2012-08-15 | 常州大学 | Fluorine-containing waterproofing agent for textiles and method for preparing same |
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