CN103788316B - Fluorinated block copolymer and application thereof - Google Patents
Fluorinated block copolymer and application thereof Download PDFInfo
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- CN103788316B CN103788316B CN201410072075.0A CN201410072075A CN103788316B CN 103788316 B CN103788316 B CN 103788316B CN 201410072075 A CN201410072075 A CN 201410072075A CN 103788316 B CN103788316 B CN 103788316B
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Abstract
<b>the present invention relates to a kind of fluorinated block copolymer, be obtained by reacting by polymerization single polymerization monomer is aggregated, polymerization single polymerization monomer by</b><b>15% ~ 65%</b><b>monomer</b><b>a</b><b>,</b><b>1% ~ 10%</b><b>monomer</b><b>d</b><b>and all the other are monomer</b><b>b</b><b>with</b><b>/</b><b>or</b><b>c</b><b>composition,</b><b>monomer</b><b>a</b><b>formula be</b><b>cH2=C(x)-COO-CH2CH2-Rf</b><b>,</b><b>x</b><b>for</b><b>h</b><b>,</b><b>cl</b><b>,</b><b>f</b><b>or</b><b>cH3</b><b>；</b><b>rf</b><b>for perfluoro hexyl or perfluoro butyl；Monomer</b><b>b</b><b>for the crystallizable alkyl acrylate of alkyl side chain or alkyl methacrylate；Monomer</b><b>c</b><b>for homopolymer glass transition temperature more than</b><b>60 DEG C</b><b>alkyl acrylate or alkyl methacrylate；Monomer</b><b>d</b><b>formula be</b><b>cH2=C(y)-COR1-(CH2)d-OH</b><b>,</b><b>y</b><b>for</b><b>h</b><b>or</b><b>cH3</b><b>；</b><b>r1</b><b>for</b><b>o</b><b>or</b><b>nH</b><b>；</b><b>d</b><b>for</b><b>1 ~ 6</b><b>between integer。Take the water-repellent oil-repellent agent that the present invention prepares both to have the water and oil repellent finish effect of excellence, be absent from again bio-toxicity。</b>
Description
Technical field
The present invention relates to a kind of fluorinated block copolymer and application thereof。
Background technology
Fluoro containing polymers has many excellent properties, as remarkable refuses water and oil repellency。It is well-known for being applied to prepare water-refusing oil-refusing finishing agent by the copolymer of (methyl) Perfluoroalkyl acrylate。
It is known that when the carbon number of the metha crylic comonomer perfluoroalkyl used is lower than 8, water and oil repellant processing agent occurs: even if perfluoroalkyl unit consumption is higher, the problem that water and oil repellant performance is still insufficient, and the problem that washing resistance is poor。Although and adopt the metha crylic comonomer of perfluor segment of higher carbon number (more than 8), water and oil repellant performance can be significantly improved, but, owing to the perfluor segment containing eight carbon atoms exists biological accumulation and certain bio-toxicity, presently relevant bill is promulgated, it will be implemented disabling。
Summary of the invention
The technical problem to be solved is to overcome the deficiencies in the prior art, a kind of new fluorinated block copolymer is provided, take this copolymer can prepare stable water-repellent oil-repellent agent, and prepared water-repellent oil-repellent agent had both had the water and oil repellent finish effect of excellence, was absent from again bio-toxicity。
For solving above technical problem, the present invention adopts the following technical scheme that:
A kind of fluorinated block copolymer, is obtained by reacting by polymerization single polymerization monomer is aggregated, and weight average molecular weight is 5000～100000, with weight, described polymerization single polymerization monomer by the monomer A of 15%～65%, the monomer D of 1%～10% and all the other form for monomer B and/or C,
The general structure of described monomer A is CH2=C(x)-COO-CH2CH2-Rf, in formula: x is H, Cl, F or CH3；Rf is perfluoro hexyl or perfluoro butyl；
Described monomer B is the crystallizable alkyl acrylate of alkyl side chain or alkyl methacrylate；
Described monomer C is the glass transition temperature of the homopolymer alkyl acrylate more than 60 DEG C or alkyl methacrylate；
The general structure of described monomer D is CH2=C(y)-COR1-(CH2)d-OH, in formula: y is H or CH3；R1For O or NH；D is the integer between 1～6。
Preferably, described polymerization single polymerization monomer by the monomer A of 20%～40%, the monomer D of 3%～8% and all the other form for monomer B and/or monomer C。
Preferably, the weight average molecular weight of described fluorinated block copolymer is between 20000～80000。
Further, one or more the combination that described monomer A is preferably selected from following monomer:
CH2=CH-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-CF2CF2CF2CF3。
It is highly preferred that monomer A is CH2=C(CH3)-COO-CH2CH2-CF2CF2CF2CF2CF2CF3Or CH2=C(Cl)-COO-CH2CH2-CF2CF2CF2CF2CF2CF3。
Preferably, described monomer D is one or more the combination in hydroxyethyl methylacrylate, Hydroxypropyl methacrylate, methacrylate and n-methylolacrylamide。
More specifically, the alkyl carbon chain constituting monomer B is carbon number is the straight chained alkyl of 16～24。Monomer B includes but not limited to octadecyl acrylate, octadecyl methacrylate, behenyl base ester, methacrylic acid docosyl ester, Process Conditions of Cetane Acrylate, hexadecyl metrhacrylate。
More specifically, the alkyl carbon chain constituting monomer C is carbon number is the branched alkyl of 1～6, or the alkyl containing cycloalkane structure。Monomer C includes but not limited to cyclohexyl methacrylate, isobornyl methacrylate, Tert-butyl Methacrylate。
According to the present invention, described fluorinated block copolymer can adopt polymerization well known in the art to prepare。Preferably, described fluorinated block copolymer is prepared by atom transfer radical polymerization method (ATRP)。According to a specific aspect, the preparation method of fluorinated block copolymer is as follows: be dissolved in organic solvent by any one monomer, the initiator of atom transfer radical polymerization is added in system, the metallic catalyst of atom transfer radical polymerization, the metal catalyst complex of atom transfer radical polymerization, after passing into nitrogen displacement, sealing system, it is polymerized under 10～150 DEG C of conditions, when monomer conversion reaches more than 95%, remaining monomer is imported again one by one in system, when a kind of monomer importing conversion ratio are more than 95%, import lower a kind of monomer again, until last a kind of monomer imports, and when conversion ratio is more than 99%, pass into air, terminate reaction, can by such as reactant liquor being separated off metallic catalyst through alumina filled post, obtain described fluorinated block copolymer。
In above-mentioned preparation method: organic solvent used can be the mixed solvent (90/10v/v) of toluene, dimethylbenzene, benzotrifluoride, methanol and water, methyl ethyl ketone, ethyl acetate, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, 1,4-dioxane (dioxanes), methyl phenyl ethers anisole, N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO) or isopropanol etc.。Initiator used can be alkyl halide, benzylic halides, alpha-halogen ester, α-halogenatedketone, alpha-halogen nitrile etc., and concrete initiator can be such as alpha-bromo ethyl acetate。Metallic catalyst used is preferably copper and mantoquita, is specifically as follows Cu-lyt., copper chloride, cuprous bromide, copper bromide etc.。The derivant of the preferred pyridine structure contained unit of metal catalyst complex used, the construction unit containing tertiary amine derivant, be specifically as follows bipyridyl or N, N, N', N, ' N''-five methyl diethylentriamine。
The invention still further relates to the application in preparing fabric water-repellent oil-repellent agent of the above-mentioned fluorinated block copolymer。
The present invention also provides for a kind of fabric water-repellent oil-repellent agent, and it contains above-mentioned fluorinated block copolymer。
Due to the enforcement of above technical scheme, the present invention compared with prior art has the advantage that
(1) fluorinated block copolymer of the present invention, the carbon number of the perfluoroalkyl of monomer used, lower than 8, is absent from bio-toxicity；
(2) good emulsion stability that the fluorinated block copolymer of the present invention is prepared；
(3) fluorinated block copolymer of the present invention has the water and oil repellant of excellence, can compare favourably with the water and oil repellent finish effect of copolymer prepared by the monomer with high carbon number perfluoroalkyl；
(4) the water and oil repellant effect of the fabric after the fluorinated block copolymer of the present invention arranges also has washing resistance。
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention will be further described in detail, but the present invention is not limited to following example。The implementation condition adopted in embodiment can do further adjustment according to specifically used different requirement, and not marked implementation condition is the condition in normal experiment。
Embodiment 1
The four-hole boiling flask of 500ml loads perfluoro hexyl ethylmethyl acrylate 100g, benzotrifluoride 300g, alpha bromoisobutyric acid ethyl ester 1.5g, N, N, N', N, ' N''-five methyl diethylentriamine 3.0g, cuprous bromide 2.0g, pass into nitrogen displacement, treat that oxygen content is down to below 100ppm, it is warming up to 80 DEG C, after reacting 6 hours, by gas chromatographic detection conversion ratio more than 98%；Injecting 160g octadecyl acrylate in system, temperature rises to 110 DEG C, after reacting 30 hours, by gas chromatographic detection conversion ratio more than 98%；30g isobornyl methacrylate is injected in system, after reacting 10 hours, by gas chromatographic detection conversion ratio more than 99%, again in system inject 10gN-n-methylolacrylamide, after reacting 2 hours, by gas chromatographic detection conversion ratio more than 99%, pass into air, cooling, terminating reaction, product, through alumina filled post, removes metallic catalyst。Followed the tracks of molecular weight growth pattern and molecular weight distribution by gel permeation chromatography, confirmation product is block copolymer, and weight average molecular weight is 3.5 ten thousand (polystyrene conversion), forms fluorinated block copolymer solution, and solids content is 50wt%。
Embodiment 2～6
Monomer shown in table 1 forms and proportioning, repeats the step identical with embodiment 1, finally gives the solution of 50wt% solids content, and gained fluorinated block copolymer weight average molecular weight is referring to table 1。
Table 1
Comparative example 1
The four-hole boiling flask of 500ml loads perfluoro hexyl ethylmethyl acrylate 100g, octadecyl acrylate 160g, isobornyl methacrylate 30g, N hydroxymethyl acrylamide 10g, benzotrifluoride 300g, 2g azodiisobutyronitrile, pass into nitrogen displacement, it is warming up to 80 DEG C, after reacting 20 hours, by gas chromatographic detection conversion ratio more than 98%, cooling, terminates reaction。Followed the tracks of molecular weight growth pattern and molecular weight distribution by gel permeation chromatography, confirmation product is random copolymer, and weight average molecular weight is 5.5 ten thousand (polystyrene conversion), forms fluorine-containing random copolymer solution, and solids content is 50wt%。
Comparative example 2～6
Monomer shown in table 2 forms and proportioning, repeats the step identical with comparative example 1, finally gives the solution of 50wt% solids content, and the weight average molecular weight of resulting polymers is referring to table 1。
Embodiment 1～6 and the water repellency of the copolymer of comparative example 1～6, oil repellency and stability are tested, specific as follows。
1, the modulation of processed liquid:
Solution 30 weight portion of copolymer to be measured, blocked isocyanate (MDI class blocked isocyanate) 10 weight portions, benzotrifluoride 150 weight portion are mixed to get processed liquid。
2, water and oil repellant processing method: be immersed in as described in 1 by 100% cotton drill and operate in the treatment fluid obtained, removes unnecessary treatment fluid with roll so that it is upper liquid rate is 60wt%。By this cloth under 170 DEG C of conditions, dry 90 seconds, thus complete water and oil repellant and process。These cloth is measured water and oil repellant, and result is as shown in table 3。
3, method of testing:
(1) water repellency method of testing:
A, fabric is carried out waterproof and oilproof process: fabric two soaks two and rolls finishing agent (20-50g/L, pH5.0-7.0, pick-up 70%) → roasting preliminary drying (120 DEG C, 90S) → bake and bank up with earth (150 DEG C, 3min) or (170 DEG C, 1min)；
B, water repellency are tested: use water pouring test device, in 25～30 seconds, 250ml water drench wine on measured object, observe fabric wetting state, evaluate water repellency:
100 points: surface is nonwetting, water droplet does not attach；
90 points: surface is nonwetting, but have little water droplet to attach；
80 points: there is drops moistening on surface；
70 points: there is considerable part moistening on surface；
50 points: surface is all moistenings almost；
0 point: the equal moistening of positive and negative
(2) oil repellent method of testing:
Test by AATCC-118 method。The hydrocarbon liquids homologue reduced successively using 8 kinds of surface tension is as standard, respectively various standard solutions (see table 2) are dripped on the surface of the fabric with dropper, the test liquid (refusing water grade 1 grade) minimum by numerical value, each described liquid (diameter of about 5mm or the volume of 0.05ml) on the position of three at least 5mm of being separated by。Observe described drop 30 seconds, if when this stage terminates, three dropping liquids drip in two still absorbed without along drop in spherical, then the drop of higher for next one numerical value is dripped three and drops on adjacent position and observation 30 seconds equally。Be worked on until three dropping liquids of one of them test liquid drip in two can not keep spherical to hemispherical, or there is moistening or absorption。Be generally of 5 or the treated fabric of greater degree think good in excellent；Have 1 or the fabric of greater degree can use in some applications。
Table 2 oil repellency ranking table
| Test solution | Grade |
| Liquid paraffin | 1# |
| Liquid paraffin/n-hexadecane | 2# |
| N-hexadecane | 3# |
| The n-tetradecane | 4# |
| N-dodecane | 5# |
| N-decane | 6# 4 --> |
| N-octane | 7# |
(3) washability evaluation methodology
In standard washer, adopt " Tide " board of 140g to wash adjustment at the temperature of 41 DEG C test sample to be washed 12 minutes, the sample filled by whole washing machine subsequently and ballast are placed in dryer and are dry 45 minutes at 75 DEG C at maximum air exit temp, and then dry test sample is judged by comparison water and oil repellant performance rate as mentioned above。
Further, in order to evaluate washing resistance, with AATCC method for benchmark, being 40 DEG C in water temperature, every time wash time is 12 minutes, and carries out cylinder dry, as a circulation。Processed cloth after being repeatedly performed this circulation is measured water and oil repellant。
4, test result: referring to table 3。From the data of table 3 embodiment 1～6, the fluorinated block copolymer of the present invention shows the water and oil repellant of excellence and durable washing property。Comparative example 1～6 and comparative example 1～6, it may be concluded that in the identical situation of monomeric species and consumption, the finishing effect of block copolymer is superior more than the finishing effect of random copolymer。
Table 3
Note: in table, numeral A～numeral B represents the performance in the middle of A and B；After HL10, HL20 represent washing 10 times respectively, after 20 times。
Above the present invention is described in detail; its object is to allow the personage being familiar with this art will appreciate that present disclosure and to be carried out; can not limit the scope of the invention with this; the equivalence that all spirit according to the present invention are made changes or modifies, and all should be encompassed in protection scope of the present invention。
Claims (6)
1. a fluorinated block copolymer, it is obtained by reacting by polymerization single polymerization monomer is aggregated, it is characterized in that: the weight average molecular weight of described fluorinated block copolymer is 5000 ~ 100000, with weight, described polymerization single polymerization monomer by the monomer A of 15% ~ 65%, the monomer D of 1% ~ 10% and all the other form for monomer B and C
Described monomer A is perfluoro hexyl ethylmethyl acrylate or perfluoro butyl ethyl α-chloro-acrylicacid ester；
Described monomer B is octadecyl acrylate；
Described monomer C is isobornyl methacrylate；
Described monomer D is n-methylolacrylamide。
2. fluorinated block copolymer according to claim 1, it is characterised in that: described polymerization single polymerization monomer by the monomer A of 20% ~ 40%, the monomer D of 3% ~ 8% and all the other form for monomer B and monomer C。
3. fluorinated block copolymer according to claim 1, it is characterised in that: the weight average molecular weight of described fluorinated block copolymer is between 20000 ~ 80000。
4. fluorinated block copolymer according to claim 1, it is characterised in that: described fluorinated block copolymer is prepared by atom transfer radical polymerization method。
5. the application in preparing fabric water-repellent oil-repellent agent of the fluorinated block copolymer as described in a claim any one of Claims 1-4。
6. a fabric water-repellent oil-repellent agent, it is characterised in that: containing the fluorinated block copolymer described in claim any one of Claims 1-4。
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| JP7417141B2 (en) * | 2022-04-06 | 2024-01-18 | ダイキン工業株式会社 | Fluorine-containing polymers and fluorine-containing compositions |
| CN115124668B (en) * | 2022-05-16 | 2023-08-22 | 浙江传化功能新材料有限公司 | Fluorine-containing multiblock copolymer, preparation method and application thereof |
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