CN1164683C - A kind of hydrophobic fluorine-terminated polyurethane composition and its application - Google Patents
A kind of hydrophobic fluorine-terminated polyurethane composition and its application Download PDFInfo
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- CN1164683C CN1164683C CNB011039299A CN01103929A CN1164683C CN 1164683 C CN1164683 C CN 1164683C CN B011039299 A CNB011039299 A CN B011039299A CN 01103929 A CN01103929 A CN 01103929A CN 1164683 C CN1164683 C CN 1164683C
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- fluorine
- end group
- containing end
- polyurethane composition
- group polyurethane
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 23
- 239000000203 mixture Substances 0.000 title claims abstract description 22
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 21
- 230000002209 hydrophobic effect Effects 0.000 title abstract description 8
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 33
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000011737 fluorine Substances 0.000 claims abstract description 27
- 239000011248 coating agent Substances 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims abstract description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 37
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 17
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 17
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- -1 polyethylene Polymers 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 7
- 229920000570 polyether Polymers 0.000 claims description 7
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- 229920000728 polyester Polymers 0.000 claims description 6
- 239000004800 polyvinyl chloride Substances 0.000 claims description 6
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 5
- 230000002940 repellent Effects 0.000 claims description 5
- 239000005871 repellent Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 4
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims description 4
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 4
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 2
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 claims description 2
- 239000012456 homogeneous solution Substances 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 229920000193 polymethacrylate Polymers 0.000 claims description 2
- 230000005661 hydrophobic surface Effects 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 125000001153 fluoro group Chemical group F* 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000004970 Chain extender Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 3
- AQYSYJUIMQTRMV-UHFFFAOYSA-N hypofluorous acid Chemical compound FO AQYSYJUIMQTRMV-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- KIQKWYUGPPFMBV-UHFFFAOYSA-N diisocyanatomethane Chemical class O=C=NCN=C=O KIQKWYUGPPFMBV-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- KILURZWTCGSYRE-LNTINUHCSA-K (z)-4-bis[[(z)-4-oxopent-2-en-2-yl]oxy]alumanyloxypent-3-en-2-one Chemical compound CC(=O)\C=C(\C)O[Al](O\C(C)=C/C(C)=O)O\C(C)=C/C(C)=O KILURZWTCGSYRE-LNTINUHCSA-K 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000012660 binary copolymerization Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000009408 flooring Methods 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 239000005267 main chain polymer Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- CBFCDTFDPHXCNY-UHFFFAOYSA-N octyldodecane Natural products CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical class OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910001062 shibuichi Inorganic materials 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 150000003384 small molecules Chemical group 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
Abstract
本发明公开了一种疏水性含氟端基聚氨酯组合物，按重量计包括如下组分：含氟端基聚氨酯20～80%，辅助组分20～80%。本发明还公开了该组合物在制备疏水性表面涂层中的应用。使用本发明的含氟端基的聚氨酯组合物，其优点是成膜性好，其表面能较低，具有优良的疏水性，适于在日常生活中应用。The invention discloses a hydrophobic fluorine-containing end-group polyurethane composition, which comprises the following components by weight: 20-80% of fluorine-containing end-group polyurethane and 20-80% of auxiliary components. The invention also discloses the application of the composition in preparing the hydrophobic surface coating. The use of the fluorine-terminated polyurethane composition of the present invention has the advantages of good film-forming property, low surface energy, excellent hydrophobicity, and is suitable for application in daily life.
Description
The present invention relates to a kind of hydrophobic polyurethane composition, relate in particular to the fluorine-containing end group polyurethane composition of a kind of hydrophobicity, the invention still further relates to the application of said composition in preparation water repellent surface coating.
For the polyurethane surface flooring that contains the fluorine functional group, because fluorine atom is the minimum material of occurring in nature surface energy, Hare etc. are at J.Phys.Chem.1954, and 236 report that the surface energy size order is-CH
2〉-CH
3〉-CF
2〉-CF
2H 〉-CF
3People such as Nishino are at Langmuir 1999,15, and 4321 have delivered the result of study that perfluor eicosane hydrocarbon is deposited to glass surface, and its surface is 119 ° with the contact angle of water, and corresponding surface free energy is 6.7mJ/m
2CF
3Group is hexagonal closs packing and is arranged in the surface, is that surface energy is minimum in all solids.Thereby fluorine can effectively reduce surface free energy, and has to the surface person's character of cohesion automatically, and its drives main chain polymer together to interface movement, thereby makes the interfacial layer different in kind in body phase character.Fluoropolymer has low surface energy, and the notion that designs from polymer designs, and fluorochemical monomer is incorporated in the urethane, makes it both have good film-forming properties, has and has lower surface energy.
But, the surface of fluorin radical is only arranged, the reduction of its surface energy is limited, after taking certain special surface working, if can form staggered miscellaneous two-dimentional phase region of different nature (being roughness),, show conventional interface rerum natura on the macroscopic view at surperficial microcell under certain condition.Microcosmos geometric shape complementary on specific surface (as protruding and recessed alternate) interface structure, because the surface of indentation can make the adsorption gas molecule stable existence, so on macro surface, be equivalent to the gas membrane that has one deck stable, water can't directly be contacted with the surface of material, thereby make the surface hydrophobicity of material stronger, at this moment water droplet and interface contact angle are tending towards maximum value.
People such as Nakajima by subliming method, prepare hydrophobic porous aluminum or silicon fiml with aluminium acetylacetonate at Adv.Mater 1999,1365 report, through repeatedly apply, sintering makes porous aluminium or silicon fiml, surfaceness is introduced CF again at 100-300nm
3(CF
2)
7CH
2CH
2Si (OCH
3)
3As water-resisting agent, the preparation hydrophobic film, with the contact angle of water be 150.3 °.
People such as Ogawa are at Jpn.J.Appl.Phys.1993, and 32, the L614 report makes fluochloride silane be deposited on glass surface by method for etching plasma, has prepared hydrophobic film.
People such as Hozumi report the method with vapour deposition in Thin Solid Films 1997,303,222, pilot-gas pressure and base reservoir temperature are used fluorosilicone, and accurately control surface roughness 9.4-60.8nm makes hydrophobic membrane.
People such as Shibuichi by control alkyl ketone (AKD) crystalline growth velocity, form uneven surface at J.Phys.Chem 1996,100.19512 reports, also can prepare hydrophobic surface.
Though aforesaid method can prepare hydrophobic surface, because its complex process, or the Temperature Influence that forms, limit hydrophobic surface application in daily life greatly.
The object of the present invention is to provide a kind of good hydrophobic fluorine-containing end group polyurethane composition that has.
The present invention also aims to provide the application of a kind of fluorine-containing end group polyurethane composition in preparation water repellent surface coating.
The fluorine-containing end group polyurethane composition of a kind of hydrophobicity of the present invention comprises following component by weight:
Fluorine-containing end group urethane 20～80%
Auxiliary component 20～80%
Described auxiliary component is polystyrene (PS), polymethacrylate polymkeric substance ((CH
2C (CH
3) COOR-), polyacrylate polymers (CH
2CHCOOR-), polyethylene (PE), acrylonitrile-butadiene-styrene copolymer (ABS), polypropylene (PP), polyvinyl chloride (PC), styrene-butadiene-styrene multipolymer (SBS), poly-along divinyl (PB), polyester (PET/PBT) or its mixture.
Described fluorine-containing end group urethane has following general formula: PU-[O (CH
2)
m(CF
2)
nCF
3]
xWherein PU represents after vulcabond and polyether glycol or the polyester glycol polymerization polyether-type or the PAUR that forms through amine or pure chain extension again, the n value is 3～20, the m value is 0～12, x=2～6, can prepare as follows: in the presence of one-ended hydroxy fluorine alcohol, vulcabond and polyethers or polyester glycol and chainextender are carried out copolyreaction, described one-ended hydroxy fluorine alcohol is the compound or derivatives thereof with following general formula: CF
3(CF
2)
n(CH
2)
mOH, wherein the n value is 3～20, the m value is 0～12; The polymerization of vulcabond and polyether glycol is 50～120 ℃ of following polymerizations, and its mole proportioning is 1.0: 0.2～1.0: 1.0; The weight percentage of described one-ended hydroxy fluorine alcohol is 1～20%; Described chainextender is small molecules glycol HO-R-OH, how pure R '-(OH)
m, small molecules diamines NH
2-R-NH
2Or polyamines R '-(NH
2)
m, wherein, R=C
nH
2n, R '=C
nH
2n-m, n=1～10, m=0～6; Described vulcabond is preferably ditan-4,4 '-vulcabond (MDI), tolylene diisocyanate (TDI), six methylene diisocyanates (HDI) or derivatives thereof.Described polyether glycol is preferably molecular weight M=1.0 * 10
2～1.0 * 10
5Polytetramethylene ether glycol, polypropylene oxide glycol, polyoxyethylene oxypropylene copolyether glycol, tetrahydrofuran (THF)-propylene oxide binary copolymerization ether glycol, tetrahydrofuran (THF)-propylene oxide-oxyethane terpolymer ether glycol.Described polyester glycol is molecular weight M=1.0 * 10
2～1.0 * 10
5Viscotrol C, poly-epsilon-caprolactone glycol and hexanodioic acid and the polymkeric substance of ethylene glycol, propylene glycol, butyleneglycol or their mixture.Can further contain dimethyl formamide, methylethylketone, toluene, ethyl acetate, tetrahydrofuran (THF) or its mixed solvent in the described reaction.Described reaction can further contain catalyzer, and described catalyzer is dibutyl tin laurate, stannous octoate, triethylenediamine.
The application of a kind of fluorine-containing end group polyurethane composition of the present invention in preparation water repellent surface coating, be included in the fluorine-containing end group polyurethane composition and add solvent, be heated to 60-120 ℃, making two components dissolved is transparent and homogeneous solution, get this drips of solution then 10-50 ℃ of following film forming, described solvent is tetrahydrofuran (THF), N, N '-dimethyl formamide, toluene, methylethylketone, vinyl-acetic ester or their mixed solvent.Described fluorine-containing end group polyurethane composition in described solution by weight preferred content be 2～15%.
The present invention uses the urethane of fluorine-containing end group, and its advantage is a good film-forming property, and its surface energy is lower, has good hydrophobicity, is suitable for using in daily life.In addition, consider that when the fluorochemical urethane that uses homogeneous carried out film forming, because the planeness height of film, hydrophobicity was restricted.In order to improve surface property, introduce to form when auxiliary components makes film forming being separated, cause uneven surface, make hydrophobicity also along with enhancing.
The size of material and water contact angle is to characterize surface hydrophobicity and hydrophilic conventional means, in general, contact angle is lower than 90 ° and is water-wetted surface, and contact angle is higher than 90 ° for hydrophobic surface, the conventional polyurethanes surface contact angle is about 105 °, and fluorine-containing end group polyurethane surface contact angle of the present invention can reach more than 140 °, shows strong-hydrophobicity.The atomic force microscope photo can obviously be found out scraggly rough surface structure.
Embodiment 1:
With 2000 gram molecular weights is the fluorine alcohol CF of 2000 polytetrahydrofuran polyether glycol (PTMG) and 93 gram one-ended hydroxy
3(CF
2)
7CH
2CH
2OH, 120 ℃ of preheatings 1 hour add in the reactor under argon shield, are cooled to 60 ℃.Add 500 gram methyl diphenylene diisocyanates (MDI) (being made into concentration and being 10% N, dinethylformamide (DMF) solution), 80 ℃ were stirred 2 hours down.Dropwise adding concentration under 20 ℃ is butanediamine 70 grams of 0.025g/ml dimethyl formamide solution, stir reaction down 0.5 hour, 90 ℃ were continued reaction after 30 minutes, added 2500 gram polymethylmethacrylates (PMMA) (molecular weight 200000), add N, N '-dimethyl formamide 56000 grams, the content that makes polymkeric substance are at 8% (weight meter), and 80 ℃ are stirred down, stirring velocity is 120 rev/mins, make it to be clear solution, after treating to dissolve fully, 25 ℃ of following drying and forming-films.
According to the principle of XPS, by changing input angle, can obtain the fluorine atom content of the different surfaces degree of depth, the fluorine content on the more shallow top layer of low angle reflection, the fluorine content of layer is deeply felt in the high angle reflection.When the XPS of above-mentioned product test, when input angle was 30 °, fluorine atom content was 63.56%; When input angle was 90 °, the content of fluorine atom was 60.73%, this shows, fluorine atom is higher than deep layer in the concentration on top layer, had proved the surface enrichment trend of fluorine atom.
The surface contact angle test shows, this surface contact angle is 140 °, shows strong-hydrophobicity.The surface atom force microscope is observed can have scraggly two-dimentional coarse structure by the table of discovery mask.
Embodiment 2
Clean and with the saturated reactor that is equipped with nitrogen protection pipe, thermometer, electric blender of nitrogen, add PTMG 2000 grams of molecular weight 2000, the pure CF of the fluorine of one-ended hydroxy
3(CF
2)
6CH
2CH
2OH21 gram, 120 ℃ of preheatings 1 hour add methyl diphenylene diisocyanate 263 grams through preheating under 80 ℃ of stirrings, stirring reaction adds chainextender butanediamine 44 grams, is stirred to reaction rapidly and finishes, add 1000 gram polystyrene (PS) (molecular weight 100000), add tetrahydrofuran (THF) 33000 grams, the content that makes polymkeric substance is at 10% (weight meter), and 100 ℃ are stirred down, stirring velocity is 120 rev/mins, make it to be clear solution, after treating to dissolve fully, 45 ℃ of following drying and forming-films.
Surface contact angle test shows, this surface contact angle are 141 °.
Embodiment 3
With molecular weight is 2000 polytetrahydrofuran polyether glycol, 2000 grams; methyl diphenylene diisocyanate 1250 grams; under argon shield, add in the reactor; heat 80 ℃ and also stir; progressively add solvent dimethyl formamide 6000ml in 2 hours; add butyleneglycol 45 grams down at 30 ℃, stir reaction down 0.5 hour, 70 ℃ of fluorine alcohol CF that add one-ended hydroxy down
3(CF
2)
8CH
2CH
2OH 257 grams; stirring and argon shield were reacted 30 minutes down, dripped 68 in 50 ℃ and restrained tetramethylolmethanes (being made into the dimethyl formamide solution of 0.05g/ml concentration), and reaction adds butanediamine 220 and restrains reaction to finishing after half hour; add 2100 gram polyvinyl chloride (PC); add methylethylketone 57000 grams, the content that makes polymkeric substance is at 9% (weight meter), and 110 ℃ are stirred down; stirring velocity is 120 rev/mins; make it to be clear solution, after treating to dissolve fully, 35 ℃ of following drying and forming-films.
Surface contact angle test shows, this surface contact angle are 143 °.
Claims (3)
1. fluorine-containing end group polyurethane composition of hydrophobicity comprises following component by weight:
Fluorine-containing end group urethane 20～80%
Auxiliary component 80～20%
Described fluorine-containing end group urethane has following general formula: PU-[O (CH
2)
m(CF
2)
nCF
3]
x, wherein PU represents after vulcabond and polyether glycol or the polyester glycol polymerization polyether-type or the PAUR that forms through amine or pure chain extension again, and the n value is 3～20, and the m value is 0～12, x=2～6;
Described auxiliary component is polystyrene (PS), polymethacrylate polymkeric substance ((CH
2C (CH
3) COOR-), polyacrylate polymers (CH
2CHCOOR-), polyethylene (PE), acrylonitrile-butadiene-styrene copolymer (ABS), polypropylene (PP), polyvinyl chloride (PC), styrene-butadiene-styrene multipolymer (SBS), poly-along divinyl (PB), polyester (PET/PBT) or its mixture.
2. the application of fluorine-containing end group polyurethane composition in preparation water repellent surface coating, in comprising the fluorine-containing end group polyurethane composition described in the claim 1, add solvent, be heated to 60-120 ℃, making two components dissolved is transparent and homogeneous solution, get this solution then 10-50 ℃ of following film forming, described solvent can be tetrahydrofuran (THF), N, N '-dimethyl formamide, toluene, methylethylketone, vinyl-acetic ester or their mixed solvent.
3. the fluorine-containing end group polyurethane composition application in preparation water repellent surface coating, it is characterized in that described fluorine-containing end group polyurethane composition in described solution by weight content be 2～15%.
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|---|---|---|---|
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|---|---|---|---|
| CNB011039299A CN1164683C (en) | 2001-02-15 | 2001-02-15 | A kind of hydrophobic fluorine-terminated polyurethane composition and its application |
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| Publication Number | Publication Date |
|---|---|
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| CN1164683C true CN1164683C (en) | 2004-09-01 |
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| CA2593694A1 (en) * | 2004-12-30 | 2006-07-13 | 3M Innovative Properties Company | Articles comprising a fluorochemical surface layer and related methods |
| CN101275054B (en) * | 2007-03-29 | 2012-06-20 | 比亚迪股份有限公司 | Ultraviolet cured paint composition and preparation thereof |
| DE102007015450A1 (en) * | 2007-03-30 | 2008-10-02 | Siemens Ag | Coating for steam condensers |
| CN100593557C (en) * | 2008-01-31 | 2010-03-10 | 中国科学院化学研究所 | Anti-icing coatings and methods of use thereof |
| CN103396608B (en) * | 2013-07-12 | 2015-09-09 | 安徽安远塑胶股份有限公司 | A kind of anti-aging plastic and preparation method thereof |
| CN107495490A (en) * | 2017-08-25 | 2017-12-22 | 温州市金鸳鸯服装有限公司 | Western-style clothes with waterproof and breathable performance and preparation method thereof |
| EP3713979B1 (en) * | 2017-11-23 | 2024-03-06 | Solvay Specialty Polymers Italy S.p.A. | Medical devices |
| CN109608974B (en) * | 2018-10-26 | 2020-09-18 | 合肥科天水性科技有限责任公司 | Fluorinated waterborne polyurethane and preparation method and application thereof |
| CN113088169A (en) * | 2021-03-31 | 2021-07-09 | 惠州市浩明科技股份有限公司 | Polyurethane waterproof coating |
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2001
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