CN103788316A - Fluorine-containing block copolymer and application thereof - Google Patents
Fluorine-containing block copolymer and application thereof Download PDFInfo
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- CN103788316A CN103788316A CN201410072075.0A CN201410072075A CN103788316A CN 103788316 A CN103788316 A CN 103788316A CN 201410072075 A CN201410072075 A CN 201410072075A CN 103788316 A CN103788316 A CN 103788316A
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Abstract
The invention relates to a fluorine-containing block copolymer which is obtained through polymerization reaction of a polymerization monomer. The polymerization monomer consists of 15%-65% of monomer A, 1%-10% of monomer D and the balance of monomer B and/or monomer C, wherein a general formula of the monomer A is CH2=C(x)-COO-CH2CH2-Rf, the x represents H, Cl, F or CH3, and the Rf represents tridecafluorohexyl or perfluoro butyl. The monomer B is acrylic acid alkyl ester or methacrylic acid alkyl ester with crystallizable alkyl side chain. The monomer C is acrylic acid alkyl ester or methacrylic acid alkyl ester with homopolymer glass-transition temperature larger than 60 DEG C. A general formula of the monomer D is CH2=C(y)-COR1-(CH2)d-OH, wherein the y represents H or CH3, the R1 represents O or NH, and the d is an integer ranging from 1 to 6. A water-repellent oil-repellent agent prepared by adopting the fluorine-containing block copolymer has excellent water-repellent oil-repellent finishing effect and is free of biotoxicity.
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, refuses water and oil repellent energy as brilliance.The multipolymer of (methyl) vinylformic acid perfluoro alkyl ethyl is applied to to prepare water-refusing oil-refusing finishing agent be well-known.
Known, when the carbon number of the metha crylic comonomer perfluoroalkyl using is lower than 8 time, water and oil repellant machining agent occurs: even if perfluoroalkyl unit consumption is higher, water and oil repellant performance is inadequate problem still, and the poor problem of washing resistance.Although and adopt the metha crylic comonomer of perfluor segment of higher carbon number (more than 8), can obviously improve water and oil repellant performance, but, owing to having biological accumulation and certain bio-toxicity containing the perfluor segment of eight carbon atoms, relevant bill is promulgated at present, will implement forbidding to it.
Summary of the invention
Technical problem to be solved by this invention is to overcome the deficiencies in the prior art, a kind of new fluorinated block copolymer is provided, take this multipolymer can prepare stable water-repellent oil-repellent agent, and prepared water-repellent oil-repellent agent had both had excellent water and oil repellent finish effect, there is not again bio-toxicity.
For solving above technical problem, the present invention takes following technical scheme:
A kind of fluorinated block copolymer, is obtained through polyreaction by polymerization single polymerization monomer, and weight-average molecular weight is 5000～100000, and in weight percentage, described polymerization single polymerization monomer is made up of for monomers B and/or C 15%～65% monomer A, 1%～10% monomer D and all the other,
The general structure of described monomer A is CH
2=C (x)-COO-CH
2cH
2-Rf, in formula: x is H, Cl, F or CH
3; Rf is perfluoro hexyl or perfluoro butyl;
Described monomers B is the crystallizable alkyl acrylate of alkyl group side chain or alkyl methacrylate;
Alkyl acrylate or alkyl methacrylate that the second-order transition temperature that described monomer C is homopolymer is greater than 60 ℃;
The general structure of described monomer D is CH
2=C (y)-COR
1-(CH
2)
d-OH, in formula: y is H or CH
3; R
1for O or NH; D is the integer between 1～6.
Preferably, described polymerization single polymerization monomer is made up of for monomers B and/or monomer C 20%～40% monomer A, 3%～8% monomer D and all the other.
Preferably, the weight-average molecular weight of described fluorinated block copolymer is between 20000～80000.
Further, described monomer A is preferably one or more the combination being selected from following monomer:
CH
2=CH-COO-CH
2CH
2-CF
2CF
2CF
2CF
2CF
2CF
3、CH
2=C(CH
3)-COO-CH
2CH
2-CF
2CF
2CF
2CF
2CF
2CF
3、CH
2=C(F)-COO-CH
2CH
2-CF
2CF
2CF
2CF
2CF
2CF
3、CH
2=C(Cl)-COO-CH
2CH
2-CF
2CF
2CF
2CF
2CF
2CF
3、CH
2=C(H)-COO-CH
2CH
2-CF
2CF
2CF
2CF
3、CH
2=C(CH
3)-COO-CH
2CH
2-CF
2CF
2CF
2CF
3、CH
2=C(F)-COO-CH
2CH
2-CF
2CF
2CF
2CF
3、CH
2=C(Cl)-COO-CH
2CH
2-CF
2CF
2CF
2CF
3。
More preferably, monomer A is CH
2=C (CH
3)-COO-CH
2cH
2-CF
2cF
2cF
2cF
2cF
2cF
3or CH
2=C (Cl)-COO-CH
2cH
2-CF
2cF
2cF
2cF
2cF
2cF
3.
Preferably, described monomer D is one or more the combination being selected from hydroxyethyl methylacrylate, Rocryl 410, methacrylic acid hydroxy butyl ester and n-methylolacrylamide.
More specifically, the alkyl carbon chain of formation monomers B is that carbon number is 16～24 straight chained alkyl.Monomers B includes but not limited to octadecyl acrylate, stearyl methacrylate, vinylformic acid docosyl ester, methacrylic acid docosyl ester, Process Conditions of Cetane Acrylate, methacrylic acid hexadecyl ester.
More specifically, the alkyl carbon chain that forms monomer C is that carbon number is 1～6 branched-chain alkyl, or contains the alkyl of cycloalkanes 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 process well known in the art to prepare.Preferably, described fluorinated block copolymer prepares by atom transfer radical polymerization method (ATRP).According to a concrete aspect, the preparation method of fluorinated block copolymer is as follows: any one monomer is dissolved in organic solvent, to the initiator that adds atom transfer radical polymerization in system, the metal catalyst of atom transfer radical polymerization, the metal catalyst part of atom transfer radical polymerization, pass into after nitrogen replacement, sealing system, polymerization under 10～150 ℃ of conditions, reach 95% when above until monomer conversion, in system, import one by one remaining monomer again, when a kind of monomer imports and transformation efficiency exceedes 95%, import again lower a kind of monomer, until last a kind of monomer imports, and when transformation efficiency is greater than 99%, pass into air, termination reaction, can be by for example reaction solution being separated and removes metal catalyst through alumina filled post, obtain described fluorinated block copolymer.
In above-mentioned preparation method: organic solvent used can be mixed solvent (90/10v/v), methyl ethyl ketone, ethyl acetate, dipropylene glycol monomethyl ether, dipropylene glycol, the tripropylene glycol, 1 of toluene, dimethylbenzene, phenylfluoroform, methyl alcohol and water, 4-dioxane (dioxan), methyl-phenoxide, DMF (DMF), methyl-sulphoxide (DMSO) or Virahol etc.Initiator used can be haloalkane, benzyl halide compound, alpha-halogen ester, α-halogenatedketone, alpha-halogen nitrile etc., and concrete initiator can be for example alpha-bromo ethyl acetate.Metal catalyst used is preferably copper and mantoquita, is specifically as follows cuprous chloride, cupric chloride, cuprous bromide, cupric bromide etc.The derivative of the preferred pyridine structure contained unit of metal catalyst part used, containing the derivative of the structural unit of tertiary amine, be specifically as follows dipyridyl or N, N, N', N, ' N''-five methyl diethylentriamine.
The invention still further relates to above-mentioned fluorinated block copolymer in the application of preparing in fabric water-repellent oil-repellent agent.
The present invention also provides 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 tool has the following advantages:
(1) fluorinated block copolymer of the present invention, lower than 8, there is not bio-toxicity in the carbon number of the perfluoroalkyl of monomer used;
(2) good emulsion stability that fluorinated block copolymer of the present invention is prepared;
(3) fluorinated block copolymer of the present invention has excellent water and oil repellant, and the water and oil repellent finish effect of the multipolymer that can prepare with the monomer with high carbon number perfluoroalkyl compares favourably;
(4) the water and oil repellant effect of the fabric after fluorinated block copolymer of the present invention arranges also has washing resistance.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described in detail, but the present invention is not limited to following examples.The implementation condition adopting in embodiment can require to do further adjustment according to the difference of concrete use, and not marked implementation condition is the condition in normal experiment.
Embodiment 1
In the four-hole boiling flask of 500ml, pack perfluoro hexyl ethyl-methyl acrylate 100g, phenylfluoroform 300g, alpha bromoisobutyric acid ethyl ester 1.5g, N into, N, N', N, ' N''-five methyl diethylentriamine 3.0g, cuprous bromide 2.0g, pass into nitrogen replacement, treat that oxygen level is down to below 100ppm, be warming up to 80 ℃, react after 6 hours, be greater than 98% by gas chromatographic detection transformation efficiency; In system, inject 160g octadecyl acrylate, temperature rises to 110 ℃, reacts after 30 hours, is greater than 98% by gas chromatographic detection transformation efficiency; In system, inject 30g isobornyl methacrylate, react after 10 hours, be greater than 99%, in system, inject 10g N hydroxymethyl acrylamide again by gas chromatographic detection transformation efficiency, react after 2 hours, be greater than 99% by gas chromatographic detection transformation efficiency, pass into air, cooling, termination reaction, product, through alumina filled post, is removed metal catalyst.Follow the tracks of molecular weight growth pattern and molecular weight distribution by gel permeation chromatography, confirmation product is segmented 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
According to the monomer composition shown in table 1 and proportioning, repeat the step identical with embodiment 1, finally obtain the solution of 50wt% solids content, gained fluorinated block copolymer weight-average molecular weight is referring to table 1.
Table 1
Comparative example 1
In the four-hole boiling flask of 500ml, pack perfluoro hexyl ethyl-methyl acrylate 100g, octadecyl acrylate 160g, isobornyl methacrylate 30g, N hydroxymethyl acrylamide 10g, phenylfluoroform 300g, 2g Diisopropyl azodicarboxylate into, pass into nitrogen replacement, be warming up to 80 ℃, react after 20 hours, be greater than 98% by gas chromatographic detection transformation efficiency, cooling, termination reaction.Follow the tracks of molecular weight growth pattern and molecular weight distribution by gel permeation chromatography, confirmation product is random copolymers, and weight-average molecular weight is 5.5 ten thousand (polystyrene conversion), forms fluorine-containing random copolymers solution, and solids content is 50wt%.
Comparative example 2～6
According to the monomer composition shown in table 2 and proportioning, repeat the step identical with comparative example 1, finally obtain the solution of 50wt% solids content, the weight-average molecular weight of resulting polymers is referring to table 1.
Water repellency, oil repellent energy and the stability of the multipolymer to embodiment 1～6 and comparative example 1～6 are tested, specific as follows.
1, the modulation of processing treatment liquid:
The solution of multipolymer to be measured 30 weight parts, masked isocyanate (MDI class masked isocyanate) 10 weight parts, phenylfluoroform 150 weight parts are mixed to get to processing treatment liquid.
2, water and oil repellant treatment process: 100% cotton drill is immersed in the treatment solution that operation obtains as described in 1, removes unnecessary treatment solution with roll, making liquid rate on it is 60wt%.This cloth, under 170 ℃ of conditions, dry 90 seconds, is completed to water and oil repellant processing thus.These cloth are measured to water and oil repellant, and result is as shown in table 3.
3, testing method:
(1) water repellency testing method:
A, fabric is carried out to waterproof and oilproof processing: fabric two soaks two and rolls finishing composition (20-50g/L, pH5.0-7.0, pick-up 70%) → roasting preliminary drying (120 ℃, 90S) → bake and bank up with earth (150 ℃, 3min) or (170 ℃, 1min);
B, water repellency test: use sprinkling test equip, in 25～30 seconds, 250ml water is drenched to wine on analyte, observe fabric wetting regime, evaluation water repellency:
100 points: surface is nonwetting, and water droplet does not attach;
90 points: surface is nonwetting, but has little water droplet to attach;
80 points: surface has drops wetting;
70 points: surface has considerable part wetting;
50 points: surface is almost all wetting;
0 point: pros and cons is all wetting
(2) oil repellent testing method:
Test by AATCC-118 method.The hydrocarbon liquids homologue reducing successively using 8 kinds of surface tension is as standard, respectively various standard solutions (in table 2) are dropped on fabric face with dropper, started each described liquid (the approximately diameter of 5mm or the volume of 0.05ml) on the position of three 5mm at least of being separated by by the minimum test liquid of numerical value (refusing 1 grade of water grade).Observe described drop 30 seconds, if in the time that this stage finishes, during three dropping liquids drip two are still spherical and are not absorbed along drop, the drop of the higher numerical value of the next one are dripped to three and drop on adjacent position and same observation 30 seconds.Proceed operation until in dripping two of three dropping liquids of one of them test liquid can not keep spherical to semisphere, or occur wetting or absorb.Conventionally have 5 or more high-grade treated fabric think good in excellent; Have 1 or more high-grade fabric can use in some applications.
Table 2 oil repellent energy ranking table
| Test solution | Grade |
| Whiteruss | 1# |
| Whiteruss/n-n-Hexadecane | 2# |
| N-n-Hexadecane | 3# |
| The n-tetradecane | 4# |
| N-dodecane | 5# |
| N-decane | 6# |
| N-octane | 7# |
(3) washing fastness evaluation method
In standard washer, at the temperature of 41 ℃, adopt " Tide " board of 140g to wash adjustment and will test sample washing 12 minutes, it is to be dried 45 minutes at 75 ℃ that the sample subsequently whole washing machine being filled and ballast weight are placed in clothes-drying machine and at maximum air exit temp, and then contrast water and oil repellant performance rate is judged dry test sample as mentioned above.
And, in order to evaluate washing resistance, take AATCC method as benchmark, be 40 ℃ in water temperature, every time washing time is 12 minutes, and carries out roller drying, as a circulation.The processed cloth repeatedly carrying out after this circulation is measured to water and oil repellant.
4, test result: referring to table 3.From the data of table 3 embodiment 1～6, fluorinated block copolymer of the present invention shows excellent water and oil repellant and durable washing property.Comparative example 1～6 and comparative example 1～6, can reach a conclusion: in monomeric species and the identical situation of consumption, the finishing effect of segmented copolymer is superior more than the finishing effect of random copolymers.
Table 3
Note: digital A in table～digital B represents the performance in the middle of A and B; HL10, HL20 represent respectively to wash after 10 times, after 20 times.
Above the present invention is described in detail; its object is to allow the personage who is familiar with this art can understand content of the present invention and be implemented; can not limit the scope of the invention with this; the equivalence that all spirit according to the present invention are done changes or modifies, and all should be encompassed in protection scope of the present invention.
Claims (10)
1. a fluorinated block copolymer, obtained through polyreaction by polymerization single polymerization monomer, it is characterized in that: the weight-average molecular weight of described fluorinated block copolymer is 5000～100000, in weight percentage, described polymerization single polymerization monomer is made up of for monomers B and/or C 15%～65% monomer A, 1%～10% monomer D and all the other
The general structure of described monomer A is CH
2=C (x)-COO-CH
2cH
2-Rf, in formula: x is H, Cl, F or CH
3; Rf is perfluoro hexyl or perfluoro butyl;
Described monomers B is the crystallizable alkyl acrylate of alkyl group side chain or alkyl methacrylate;
Alkyl acrylate or alkyl methacrylate that the second-order transition temperature that described monomer C is homopolymer is greater than 60 ℃;
The general structure of described monomer D is CH
2=C (y)-COR
1-(CH
2)
d-OH, in formula: y is H or CH
3; R
1for O or NH; D is the integer between 1～6.
2. fluorinated block copolymer according to claim 1, is characterized in that: described polymerization single polymerization monomer is made up of for monomers B and/or monomer C 20%～40% monomer A, 3%～8% monomer D and all the other.
3. fluorinated block copolymer according to claim 1, is characterized in that: the weight-average molecular weight of described fluorinated block copolymer is between 20000～80000.
4. fluorinated block copolymer according to claim 1, is characterized in that: described monomer A is one or more the combination being selected from following monomer:
CH
2=CH-COO-CH
2CH
2-CF
2CF
2CF
2CF
2CF
2CF
3、CH
2=C(CH
3)-COO-CH
2CH
2-CF
2CF
2CF
2CF
2CF
2CF
3、CH
2=C(F)-COO-CH
2CH
2-CF
2CF
2CF
2CF
2CF
2CF
3、CH
2=C(Cl)-COO-CH
2CH
2-CF
2CF
2CF
2CF
2CF
2CF
3、CH
2=C(H)-COO-CH
2CH
2-CF
2CF
2CF
2CF
3、CH
2=C(CH
3)-COO-CH
2CH
2-CF
2CF
2CF
2CF
3、CH
2=C(F)-COO-CH
2CH
2-CF
2CF
2CF
2CF
3、CH
2=C(Cl)-COO-CH
2CH
2-CF
2CF
2CF
2CF
3。
5. fluorinated block copolymer according to claim 1, is characterized in that: described monomer D is one or more the combination being selected from hydroxyethyl methylacrylate, Rocryl 410, methacrylic acid hydroxy butyl ester and n-methylolacrylamide.
6. fluorinated block copolymer according to claim 1, is characterized in that: the alkyl carbon chain that forms described monomers B is that carbon number is 16～24 straight chained alkyl; The alkyl carbon chain that forms described monomer C is that carbon number is 1～6 branched-chain alkyl, or contains the alkyl of cycloalkanes structure.
7. fluorinated block copolymer according to claim 6, is characterized in that: described monomers B comprises octadecyl acrylate, stearyl methacrylate, vinylformic acid docosyl ester, methacrylic acid docosyl ester, Process Conditions of Cetane Acrylate, methacrylic acid hexadecyl ester; Described monomer C comprises cyclohexyl methacrylate, isobornyl methacrylate, Tert-butyl Methacrylate.
8. fluorinated block copolymer according to claim 1, is characterized in that: described fluorinated block copolymer prepares by atom transfer radical polymerization method.
9. the fluorinated block copolymer as described in any one claim in claim 1 to 8 is in the application of preparing in fabric water-repellent oil-repellent agent.
10. a fabric water-repellent oil-repellent agent, is characterized in that: contain the fluorinated block copolymer described in any one claim in claim 1 to 8.
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|---|---|---|---|
| CN201410072075.0A CN103788316B (en) | 2014-02-28 | 2014-02-28 | Fluorinated block copolymer and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410072075.0A CN103788316B (en) | 2014-02-28 | 2014-02-28 | Fluorinated block copolymer and application thereof |
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|---|---|
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| CN103788316B CN103788316B (en) | 2016-06-22 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020196373A1 (en) * | 2019-03-25 | 2020-10-01 | 日油株式会社 | Block copolymer, release agent composition, release layer, and release sheet |
| CN115124668A (en) * | 2022-05-16 | 2022-09-30 | 浙江传化功能新材料有限公司 | Fluorine-containing multi-block copolymer and preparation method and application thereof |
| WO2023195225A1 (en) * | 2022-04-06 | 2023-10-12 | ダイキン工業株式会社 | Fluorine-containing polymer and fluorine-containing composition |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013027679A1 (en) * | 2011-08-24 | 2013-02-28 | 旭硝子株式会社 | Fluorine-containing block copolymer, method for producing same, and surface treatment agent |
-
2014
- 2014-02-28 CN CN201410072075.0A patent/CN103788316B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013027679A1 (en) * | 2011-08-24 | 2013-02-28 | 旭硝子株式会社 | Fluorine-containing block copolymer, method for producing same, and surface treatment agent |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020196373A1 (en) * | 2019-03-25 | 2020-10-01 | 日油株式会社 | Block copolymer, release agent composition, release layer, and release sheet |
| JPWO2020196373A1 (en) * | 2019-03-25 | 2020-10-01 | ||
| CN112996663A (en) * | 2019-03-25 | 2021-06-18 | 日油株式会社 | Block copolymer, release agent composition, release layer, and release sheet |
| JP7296060B2 (en) | 2019-03-25 | 2023-06-22 | 日油株式会社 | Block copolymers, release compositions, release layers, and release sheets |
| CN112996663B (en) * | 2019-03-25 | 2023-10-27 | 日油株式会社 | Block copolymer, release agent composition, release layer, and release sheet |
| TWI837330B (en) * | 2019-03-25 | 2024-04-01 | 日商日油股份有限公司 | Block copolymers, release agent compositions, release layers and release sheets |
| WO2023195225A1 (en) * | 2022-04-06 | 2023-10-12 | ダイキン工業株式会社 | Fluorine-containing polymer and fluorine-containing composition |
| JP2023154271A (en) * | 2022-04-06 | 2023-10-19 | ダイキン工業株式会社 | Fluorine-containing polymer and fluorine-containing composition |
| 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 |
| CN115124668A (en) * | 2022-05-16 | 2022-09-30 | 浙江传化功能新材料有限公司 | Fluorine-containing multi-block copolymer and preparation method and application thereof |
| 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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| Publication number | Publication date |
|---|---|
| CN103788316B (en) | 2016-06-22 |
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