CN102888752B - Water-repellent agent of fluorine-containing polymer - Google Patents
Water-repellent agent of fluorine-containing polymer Download PDFInfo
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- CN102888752B CN102888752B CN201110201910.2A CN201110201910A CN102888752B CN 102888752 B CN102888752 B CN 102888752B CN 201110201910 A CN201110201910 A CN 201110201910A CN 102888752 B CN102888752 B CN 102888752B
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- fluoropolymer
- dryingagent
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- acid
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 19
- 239000011737 fluorine Substances 0.000 title claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 title abstract description 22
- 229920000642 polymer Polymers 0.000 title abstract description 16
- 239000005871 repellent Substances 0.000 title abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 108
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 48
- 125000002091 cationic group Chemical group 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 16
- 150000007513 acids Chemical class 0.000 claims abstract description 12
- 239000004811 fluoropolymer Substances 0.000 claims description 47
- 229920002313 fluoropolymer Polymers 0.000 claims description 47
- 239000002274 desiccant Substances 0.000 claims description 38
- -1 alkyl (methyl) acrylate Chemical compound 0.000 claims description 29
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 229920001577 copolymer Polymers 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 9
- 235000019270 ammonium chloride Nutrition 0.000 claims description 8
- 125000004185 ester group Chemical group 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- AJXBTRZGLDTSST-UHFFFAOYSA-N amino 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)ON AJXBTRZGLDTSST-UHFFFAOYSA-N 0.000 claims description 5
- 150000007522 mineralic acids Chemical class 0.000 claims description 5
- 150000007524 organic acids Chemical class 0.000 claims description 5
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 5
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 150000007530 organic bases Chemical class 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 15
- 239000004744 fabric Substances 0.000 abstract description 11
- 239000002245 particle Substances 0.000 abstract description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 34
- 239000000839 emulsion Substances 0.000 description 27
- 239000003921 oil Substances 0.000 description 21
- 239000011521 glass Substances 0.000 description 19
- 239000012071 phase Substances 0.000 description 19
- 238000003756 stirring Methods 0.000 description 18
- 229910052757 nitrogen Chemical group 0.000 description 17
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000003999 initiator Substances 0.000 description 13
- 239000008346 aqueous phase Substances 0.000 description 11
- 238000001035 drying Methods 0.000 description 10
- YOIZTLBZAMFVPK-UHFFFAOYSA-N 2-(3-ethoxy-4-hydroxyphenyl)-2-hydroxyacetic acid Chemical compound CCOC1=CC(C(O)C(O)=O)=CC=C1O YOIZTLBZAMFVPK-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 8
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 8
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 8
- 238000009833 condensation Methods 0.000 description 8
- 230000005494 condensation Effects 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000010792 warming Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 6
- 239000000470 constituent Substances 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000012875 nonionic emulsifier Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000003809 water extraction Methods 0.000 description 4
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 3
- NPDACUSDTOMAMK-UHFFFAOYSA-N 4-Chlorotoluene Chemical class CC1=CC=C(Cl)C=C1 NPDACUSDTOMAMK-UHFFFAOYSA-N 0.000 description 3
- 241001044369 Amphion Species 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 3
- NQNOMXXYKHWVKR-UHFFFAOYSA-N methylazanium;sulfate Chemical compound NC.NC.OS(O)(=O)=O NQNOMXXYKHWVKR-UHFFFAOYSA-N 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical group 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 150000003871 sulfonates Chemical class 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- ZOKCNEIWFQCSCM-UHFFFAOYSA-N (2-methyl-4-phenylpent-4-en-2-yl)benzene Chemical compound C=1C=CC=CC=1C(C)(C)CC(=C)C1=CC=CC=C1 ZOKCNEIWFQCSCM-UHFFFAOYSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 description 1
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 description 1
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 1
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 description 1
- 101150037123 APOE gene Proteins 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 102100029470 Apolipoprotein E Human genes 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KIWBPDUYBMNFTB-UHFFFAOYSA-N Ethyl hydrogen sulfate Chemical group CCOS(O)(=O)=O KIWBPDUYBMNFTB-UHFFFAOYSA-N 0.000 description 1
- 239000005041 Mylar™ Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- HRKQOINLCJTGBK-UHFFFAOYSA-N dihydroxidosulfur Chemical compound OSO HRKQOINLCJTGBK-UHFFFAOYSA-N 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Paints Or Removers (AREA)
Abstract
Disclosed is a water-repellent agent of a fluorine-containing polymer. The fluorine-containing polymer includes a fluoride-containing monomer, a non-fluoride monomer and a monomer containing more than two reactive groups. The fluorine-containing polymer has excellent water-solubility. By controlling addition of different cationic emulsifiers and different acids, the magnitude of electric potential is controlled such that the fluorine-containing polymer has small particle size. When the water-repellent agent of the fluorine-containing polymer is used in fabrics, a small amount of the water-repellent agent is only required to reach an excellent water-repellent effect.
Description
Technical field
The present invention is relevant with dryingagent, refers to a kind of dryingagent of fluoropolymer in more detail.
Background technology
Dryingagent is widely used in coating or design on fabric surface process, and moisture can not be adhered to, and fluorine element polymer has the characteristic of water extraction oil extracticn agent, compares the dryingagent of silicones system, has and highly dial oily effect.
the U.S.patent US Pat.3,645,990 with US Pat.3,859,090 describes and utilizes multi-fluorinated alkyl (R
fbase) process of compound, the surface energy of the base materials such as stone material, timber, glass, pottery, fiber, metal, plastics and surface texture can be changed to give the characteristic of water-repellent oil-repellent.
taiWan, Chinapatent I301152, I302165, I304450, I304837, I325882, I332046 also once mentioned and utilized Polyfluoroalkyl R
fcrystallinity or carry out the improvement of dryingagent via other monomer upgrading, and then promote the effect of water-repellent oil-repellent.Only, mostly current technology is to inquire into and how utilizes the combination of monomer and interstructural change to improve the effect of water extraction oil extracticn agent, does not but mention the use amount of dryingagent and the relation of drying effect, therefore is necessary that the constituent character for dryingagent does assessment.
Summary of the invention
The object of the present invention is to provide a kind of dryingagent of fluoropolymer, have and on fabric, namely have excellent drying effect under low consumption.
For achieving the above object, the dryingagent of fluoropolymer provided by the invention, includes:
(A) fluorinated copolymer, the average grain diameter in the aqueous solution is 1 ~ 1000nm, and micella current potential is 0 ~ 100mV; And
(B) cationic emulsifier of two Long carbon chain alkyl of 12 ~ 22 carbon chain lengths.
The dryingagent of described fluoropolymer, wherein, this fluoropolymer is polymerized by following monomer (a1), monomer (a2) and monomer (a3), wherein:
Monomer (a1) for fluorine-containing plain monomer, its general expression be R
f-Y-X;
Wherein:
R
ffor the perfluoroalkyl of carbon number 2 ~ 20;
Y is divalent organic base or singly-bound or two isocyanide amine ester group;
X is-CR=CH
2,-C (O) OCR=CH
2,-OC (O) CR=CH
2,-OCH=CH
2,-OC
2h
4-OC (O) CR=CH
2or
r is hydrogen atom, methyl or halogen atom;
Monomer (a2) is non-fluorine element monomer, by straight chained alkyl (methyl) acrylate, branched alkyl (methyl) acrylate, and monocycle, many rings or crosslinked shape alkyl (methyl) acrylate wantonly more than two kinds of forming in group formed;
Monomer (a3) is for having the monomer of more than two reactive groups;
For this monomer (a1) 100 weight portion, this monomer (a2) is 1 ~ 300 weight portion, and this monomer (a3) is 1 ~ 50 weight portion.
The dryingagent of described fluoropolymer, wherein, cationic emulsifier is the two ammonio methacrylate of two octadecyl (flower king-D86P), two ox ester group ammonium chloride (platform circle-CNA90) or two fatty alkyl ethoxycarbonyl hydroxyethyl methyl sulfate methyl ammonium (REWOQUAT WE-18).
The dryingagent of described fluoropolymer, wherein, the better average grain diameter of this fluoropolymer is 1 ~ 200nm; The best is 1 ~ 100nm.
The manufacture method of described fluoropolymer, wherein, the better micella current potential of this fluoropolymer is 10 ~ 80mV; The best is 30 ~ 60mV.
The dryingagent of described fluoropolymer, wherein, includes acids and salt.
The dryingagent of described fluoropolymer, wherein, this acids is organic acid or inorganic acid.
The dryingagent of described fluoropolymer, wherein, this inorganic acid is hydrochloric acid, phosphoric acid or sulfuric acid.
The dryingagent of described fluoropolymer, wherein, this organic acid is acetic acid or citric acid.
When the dryingagent of fluoropolymer provided by the invention is used for fabric, only need extremely low use amount, excellent drying effect can be reached.
Detailed description of the invention
The dryingagent of fluoropolymer provided by the present invention includes:
(A) fluorinated copolymer, its average grain diameter is 1 ~ 1000nm, and micella current potential is 0 ~ 100mV; And
(B) cationic emulsifier of two Long carbon chain alkyl of 12 ~ 22 carbon chain lengths.
In an embodiment, this fluoropolymer is polymerized by following monomer (a1), monomer (a2) and monomer (a3):
Monomer (a1) for fluorine-containing plain monomer, its general expression be R
f-Y-X;
Wherein, R
ffor the perfluoroalkyl of carbon number 2 ~ 20; Y is divalent organic base or singly-bound or two isocyanide amine ester group; X is-CR=CH
2,-C (O) OCR=CH
2,-OC (O) CR=CH
2,-OCH=CH
2,-OC
2h
4-OC (O) CR=CH
2or
(R is hydrogen atom, methyl or halogen atom));
Monomer (a2) is non-fluorine element monomer, by straight chained alkyl (methyl) acrylate, branched alkyl (methyl) acrylate, and monocycle, many rings or crosslinked shape alkyl (methyl) acrylate wantonly more than two kinds of forming in group formed; And
The reactive group monomer of monomer (a3) for having more than two;
And this monomer (a1) is 100 weight portions, this monomer (a2) is 1 ~ 300 weight portion, and this monomer (a3) is 1 ~ 50 weight portion.
In an embodiment, this cationic emulsifier is the two ammonio methacrylate of two octadecyl (flower king-D86P), two ox ester group ammonium chloride (platform circle-CNA90), two fatty alkyl ethoxycarbonyl hydroxyethyl methyl sulfate methyl ammonium (REWOQUAT WE-18).
In an embodiment, the dryingagent of this fluoropolymer more includes acids and salt.
In an embodiment, this acids is hydrochloric acid, phosphoric acid, sulfuric acid, acetic acid or citric acid.
Elaborate below in conjunction with example.
The present invention inquires into and utilizes different emulsifying agents and the different acids of interpolation, observes average grain diameter, the current potential size of fluoropolymer, and then obtains the dryingagent that low consumption can reach super drying effect.
The present invention, for the formation of the fluoropolymer (A) of the dryingagent of fluoropolymer, includes following monomer (a1), monomer (a2) and monomer (a3) three kinds of compositions:
Monomer (a1) is Polyfluoroalkyl monomer, it is characterized by:
R
f-Y-X
Wherein, R
ffor the perfluoroalkyl of carbon number 2 ~ 20; Y is divalent organic base or singly-bound or two isocyanide amine ester group; X is arbitrary group-CR=CH in following formula
2,-C (O) OCR=CH
2,-OC (O) CR=CH
2,-OCH=CH
2,-OC
2h
4-OC (O) CR=CH
2or
(R is hydrogen atom, methyl or halogen atom).
Monomer (a1) preferred embodiment is
R
f-C
2H
4-OC(O)CH＝CH
2
Wherein, R
ffor the linear perfluoroalkyl of carbon number 4 ~ 16.
Raising fluorine chain length helps reduction block polymer surface energy and links crystalline substance with raising, contributes to promoting the characteristic of extremely low consumption fluouine water extraction agent, in order to keep emulsion stability to reach equalization point, and the particularly preferably R of structure
fbe 6 ~ 16 carbon numbers, the particularly R of preferred structure
fbe 8 ~ 14 carbon numbers.
Monomer (a2) is non-fluorine element monomer, includes (a2-1) straight chained alkyl (methyl) acrylate, (a2-2) branched alkyl (methyl) acrylate and (a2-3) monocycle, many rings or crosslinked shape alkyl (methyl) acrylate.In the present embodiment, this fluoropolymer is by being at least polymerized containing the repetitive of monomer of more than two kinds (a2) with monomer (a1).Following is the introduction of monomer (a2), and the constituent of its specific embodiment will be described later introduction.
(a2-1) straight chained alkyl (methyl) acrylate, its straight chain is the not fluorochemical monomer of carbon number 2 ~ 30, is preferably the not fluorochemical monomer of carbon number 12 ~ 22, is more preferred from the not fluorochemical monomer of carbon number 14 ~ 18.
(a2-2) branched-chain alkyl (methyl) acrylate, its side chain is the not fluorochemical monomer of carbon number 4 ~ 12.Specifically, be (methyl) Isooctyl acrylate monomer, (methyl) isodecyl acrylate.
(a2-3) compound at monocycle, many rings or crosslinked shape alkyl and polymerization position, the not fluorochemical monomer of its carbon number 6 ~ 20.Citing, for (methyl) isobornyl acrylate, isobornyl acrylate, t-butyl cyclohexyl ester, (methyl) acrylic acid Bicvclopentyl ester, styrene, 1,3 1-chloro-4-methyl-benzenes, Isosorbide-5-Nitrae 1-chloro-4-methyl-benzene and cyclohexyl methacrylate etc.
Monomer (a3) is for having the monomer of reactive group, and specific embodiment is shown below:
HOC
2H
4-OC(O)CR＝CH
2
R-(OC
2H
4)
m-OC(O)CR＝CH
2
R-(OC
3H
6)
m-OC(O)CR＝CH
2
NH
2-C(O)CR＝CH
2
HOC
2H
4-NH-C(O)CR＝CH
2
C
2H
6NC
2H
4-OC(O)CR＝CH
2
C
3H
9N
+(Cl
-)C
2H
4-OC(O)CR＝CH
2
ClH
2CH(OH)CH
2OC(O)CR＝CH
2
Wherein, R is the integer of hydrogen atom or methyl, m=2 ~ 50.
In fluoropolymer, relative to monomer (a1) 100 weight portion, the amount of monomer (a2) is 1 ~ 300 weight portion, and the amount of preferred monomer (a2) is 10 ~ 200 weight portions, and the amount of better monomer (a2) is 50 ~ 120 weight portions; Monomer (a3) relative quantity is 1 ~ 50 weight portion, and the amount of preferred monomer (a3) is 10 ~ 40 weight portions.
In general polymerization methods, be divided into polymerisation in solution, suspension polymerization and emulsion polymerization etc.The fluoropolymer of the present embodiment, adopts emulsion polymerization mode to prepare.
In emulsion polymerization mode, the emulsifying agent (B) used is for one or more are containing the nonionic emulsifier of APOE, cationic emulsifier and amphion emulsifying agent.
The nonionic emulsifier that the present embodiment uses is following formula:
R-X-(EO)
n-(PO)
m-H
Wherein, R is straight chain, the branched alkyl of carbon number 8 ~ 30, comprises oleic acid base; X is oxygen or nitrogen; N and m is respectively the integer of 0 ~ 50, and the summation of n and m need be greater than 3.
The embodiment of nonionic emulsifier, is exemplified as polyoxyethylene (03) bay ether (Sino-Japan chemistry SP1203), polyoxyethylene (09) bay ether (Sino-Japan chemistry SP1209), polyoxyethylene (20) bay ether (Sino-Japan chemistry SP1220), the hard ester ether of polyoxyethylene (07) (Sino-Japan chemistry SP1807), the hard ester ether of polyoxyethylene (30) (Sino-Japan chemistry SP1830), polyoxyethylene (13) oleic acid ether (Sino-Japan chemistry SP1213) etc.
The cationic emulsifier that the present embodiment uses is following formula:
(R’
4N
+)·X
-
Wherein, R ' may be hydrogen atom, the alkyl of carbon number 1 ~ 30, the alkyl group of carbon number 2 ~ 30 or EO segment, and 4 R ' can be identical, also can be not identical configuration; X is chlorine atom, ethyl sulfate ion or acetato-.
The embodiment of cationic emulsifier, is exemplified as hexadecyltrimethylammonium chloride (CTAC), octadecyl trimethyl ammonium chloride (SMTAC), the two ammonio methacrylate of two octadecyl (flower king-D86P), two ox ester group ammonium chloride (platform circle-CNA90), two fatty alkyl ethoxycarbonyl hydroxyethyl methyl sulfate methyl ammoniums (REWOQUAT WE-18) etc.
The amphion emulsifier package that the present embodiment uses is containing acid zwitterionic surfactant, polyhydric alcohol amine sulfuric acid ester, alkanamine Sulfonates interfacial agent, functionalized cationic base is ammonium salt and quarternary ammonium salt, and anionic functional base is carboxylate, sulfate and Sulfonates.
In the present embodiment, in order to control molecular weight distribution, need usage chain transfer agent (C), contain aromatic compound, sulfydryl alcohols and thio-alcohol, for carbon tetrachloride, mercaptoethanol, α-methyl styrene linear dimerization body, 2,4-diphenyl-4-methyl-1-pentene, octyl mercaptan, n-dodecyl mercaptan, tertiary lauryl mercaptan etc.
In the present embodiment in polymerisation, reactant is divided into oil phase and aqueous phase, oil phase contains monomer (a1), monomer (a2), monomer (a3), emulsifying agent (B) and chain-transferring agent (C); Aqueous phase contains water, acid, solvent.
In the present embodiment, in order to trigger reaction, initiator (D) need be used to react, contain light initiator, ion initiator and free radical starting agent, be preferably free radical starting agent, free radical starting agent contains peroxide initiator and azo-type and rises and make agent, and be more preferred from azo type initiator, polymerization temperature is preferably 40 ~ 100 DEG C.
Above-mentioned by a preferred embodiment of the present invention to prepare in the experimentation of fluoropolymer the compound introduction of participation reaction, then the particle diameter of fluoropolymer, micella current potential and controlling potential factor acids are inquired into, obtain fluoropolymer for the explanation of the preferable states when dryingagent with lower use amount.
The present embodiment is preparing and is adopting in polymerization process one or more nonionic emulsifier, cationic emulsifier and amphion emulsifying agent; First by oil phase, aqueous phase preheating after high speed dispersion before reaction, more dispersed via high pressure homogenizer, after stable even pre-emulsion can be obtained, then pre-emulsion is carried out emulsion polymerization reaction in the mode of continous mode or batch.
In the present embodiment, fluorinated copolymer is scattered in emulsion, and namely have significant effect to reach extremely low consumption, need control the particle diameter of fluorinated copolymer, preferably average grain diameter is 1 ~ 1000nm, and that better is 1 ~ 200nm, and that best is 1 ~ 100nm.When this particle size range, without the need to the consumption of too many dryingagent, good drying effect can be arrived.
In the present embodiment, fluorinated copolymer is scattered in emulsion, under different cationic emulsifiers uses, the emulsifying agent of two Long carbon chain Arrcostab chlorination ammonium type due to the ability pushing away electronics stronger, reach higher current potential, coated ability is strong, and makes fluouine water extraction agent micella have less particle diameter; Large compared with the current potential drop between high current potential and fiber, and have better attraction, and reach low consumption and just have identical effect; Draw high cationic emulsifier separately, only particle diameter is reduced helpful, and cannot current potential be promoted; And too high current potential is too strong to the adsorptivity of fiber, affects the continuation effect of following process.Namely have significant effect to reach extremely low consumption, need control the Potential distribution of micella, preferably Potential distribution is 0 ~ 100mV, and that better is 10 ~ 80mV, and that best is 40 ~ 60mV.When this potential range, only need a small amount of dryingagent, good drying effect can be arrived.
In the present embodiment, in order to control to be scattered in the Potential distribution of micella in emulsion, except emulsifying agent, also need to utilize acid (E) and salt to control suitable potential range, common acid is organic acid and inorganic acid and its esters, preferably hydrochloric acid, phosphoric acid, sulfuric acid, acetic acid, citric acid, malic acid and its esters.
The above-mentioned explanation being the fluoropolymer of a preferred embodiment of the present invention and being used for preferable states when dryingagent and lower use amount, then introduces for the occupation mode when dryingagent this fluoropolymer.
The dryingagent that fluoropolymer of the present invention is formed, can be coated with for a kind of fabric or the fiber surface of fabric blends, processing mode together can carry out with other kind of analog assistant spraying, flood or the mode of compregnate to be coated be fiber surface, again with heat treatment 100 ~ 200 DEG C, within 30 ~ 180 seconds, be cured, the effect of drying can be reached.
Above-mentioned is that the fluoropolymer of a preferred embodiment of the present invention is used for occupation mode when dryingagent, then introduces for the measurement assessment mode when dryingagent this fluoropolymer.
A. particle size measuring mode:
Weigh 1g fluorine element copolymer emulsion sample, add distilled water 199g, for subsequent use after stirring with glass rod.
Device: Malvern Instruments Ltd.Zetasizer Nano ZS90
Measure temperature: 25 DEG C (before test, sample balances 1 minute in 25 DEG C)
Correct: the NIST International Certification standard sample getting 4 Thermo, normal saline solution 100ml, after abundant mixing, get 1 ~ 1.5ml mixed liquor and put into Size cell measurement, confirm that Hydrodynamic Diameter need in scope [58 ~ 65nm (PCS)].
Test: the fluorine diluted element copolymer emulsion sample is got 1.5ml, adds in Size Cell, confirm Cell limit wall and corner all bubble-free, sample is put into ZS90 and start to measure particle diameter, carry out five loop tests, average.
B. current potential measures mode:
Weigh 1g fluorine element copolymer emulsion sample, add distilled water 199g, for subsequent use after stirring with glass rod.
Device: Malvern Instruments Ltd.Zetasizer Nano ZS90
Measure temperature: 25 DEG C (before test, sample balances 1 minute in 25 DEG C)
Correct: with alcohol, Zeta potential cell rinse is cleaned, then wash twice with distilled water, current potential standard items are injected in the middle of Cell, confirm bubble to be had in Cell, clogged by stopper, put into ZS90 and measure, potential range need at-68 ± 6.8mV.
Test: the fluorine diluted element copolymer emulsion sample is got 1.5ml, adds in Zeta potential cellrinse, confirm Cell limit wall and corner all bubble-free, sample is put into ZS90 and start to measure particle diameter, carry out five loop tests, average.
C. water-repellancy application assessment:
Cutting fabric is sanding or the spring mylar that spins of Asia or nylon cloth, and weigh fluorine element copolymer emulsion sample, thin up is 0.2 ~ 2%, the mode of dipping is utilized to make Fabric wettability,, then with the pressure of 3kg through padding machine, then with 170 DEG C, 60 seconds through setting machine.
Check the drying performance of fabric with AATCC NO.22, reference is as table 1:
The drying performance evaluation form of table 1 fabric
| Drying progression | State |
| 100 | Surface state that is not moistening or that adhere to without water droplet |
| 90 | The state of surperficial slightly water droplet attachment |
| 80 | The individual sites moisture state on surface |
| 70 | The micro-moistening state of surface half |
| 50 | The state of whole surface wettability |
| 0 | Completely moistening state |
Hereafter illustrate the embodiment of fluoropolymer of the present invention, but the present invention is not limited with these embodiments.
Following is present pre-ferred embodiments 1 ~ 4, and the constituent difference of its each embodiment is sentenced boldface letter and represented.
example 1 (as shown in table 2)
35.6g monomer (a1) R will be loaded in glass beaker
f-C
2h
2oC (O) CH=CH
2(being designated as FA below), 62.3g monomer (a2-1) octadecyl acrylate (being designated as SA below), 25.7g monomer (a2-2) EHMA (being designated as EHMA below), 6.2g monomer (a2-3) isobornyl acrylate (being designated as IBOA below), 20.2g monomer (a3) N hydroxymethyl acrylamide (being designated as N-MAM below), the hard ester ether (being designated as SP1830 below) of 7.68g emulsifying agent (B-1) polyoxyethylene (30), the hard ester ether (being designated as SP1807 below) of 2.12g emulsifying agent (B-2) polyoxyethylene (7), 7.3g emulsifying agent (B-3) hexadecyltrimethylammonium chloride (being designated as CTAC below), the tertiary lauryl mercaptan of 1.2g chain-transferring agent (being designated as TDM below) and 50g solvent dipropylene glycol methyl ether (being designated as DPM below) are oil phase, stir in 40 DEG C with homogenizer, 5g acetic acid (E) and 290g deionized water are the oil phase that aqueous phase is slowly added in high-speed stirred, stir 20 minutes after adding, by high pressure homogenizer (east China, GYB-60-6S) uniform and stable pre-emulsion is obtained for twice with 40Mpa homogeneous.
Pre-emulsion is filled to the glass four-necked bottle of agitating device, erection thermometer and condensation reflux unit, vacuumize with after nitrogen replacement 2 times, continue to pass into nitrogen, be warming up to 80 DEG C, add 1.32g initiator (V-50), to trigger polymerisation, keep 10 hours in 80 DEG C, generate polymer 493g, solid content 28.72%.
example 2 (as shown in table 2)
35.6g monomer (a1) FA will be loaded in glass beaker, 62.3g monomer (a2-1) SA, 25.7g monomer (a2-2) EHMA, 6.2g monomer (a2-3) IBOA, 20.2g monomer (a3) N-MAM, 7.68g emulsifying agent (B-1) SP1830, 2.12g emulsifying agent (B-2) SP1807, 7.68g emulsifying agent (B-3) octadecyl trimethyl ammonium chloride (being designated as STMAC below), 1.2g chain-transferring agent TDM and 50g solvent DPM is oil phase, stir in 40 DEG C with homogenizer, 5g acetic acid (E) and 290g deionized water are the oil phase that aqueous phase is slowly added in high-speed stirred, stir 20 minutes after adding, uniform and stable pre-emulsion is being obtained for twice with high pressure homogenizer 40Mpa homogeneous.
Pre-emulsion is filled to the glass four-necked bottle of agitating device, erection thermometer and condensation reflux unit, vacuumize with after nitrogen replacement 2 times, continue to pass into nitrogen, be warming up to 80 DEG C, add 1.32g initiator (V-50), to trigger polymerisation, keep 10 hours in 80 DEG C, generate polymer 486g, solid content 30.2%.
example 3 (as shown in table 2)
35.6g monomer (a1) FA will be loaded in glass beaker, 62.3g monomer (a2-1) SA, 25.7g monomer (a2-2) EHMA, 6.2g monomer (a2-3) IBOA, 20.2g monomer (a3) N-MAM, 7.68g emulsifying agent (B-1) SP1830, 2.12g emulsifying agent (B-2) SP1807, the two ammonio methacrylate (being designated as D86P below) of 7.3g emulsifying agent (B-3) two octadecyl, 1.2g chain-transferring agent TDM and 50g solvent DPM is oil phase, stir in 40 DEG C with homogenizer, 5g acetic acid (E) and 290g deionized water are the oil phase that aqueous phase is slowly added in high-speed stirred, stir 20 minutes after adding, uniform and stable pre-emulsion is being obtained for twice with high pressure homogenizer 40Mpa homogeneous.
Pre-emulsion is filled to the glass four-necked bottle of agitating device, erection thermometer and condensation reflux unit, vacuumize with after nitrogen replacement 2 times, continue to pass into nitrogen, be warming up to 80 DEG C, add 1.32g initiator (V-50), to trigger polymerisation, keep 10 hours in 80 DEG C, generate polymer 486.8g, solid content 29.6%.
example 4 (as shown in table 2)
35.6g monomer (a1) FA will be loaded in glass beaker, 62.3g monomer (a2-1) SA, 25.7g monomer (a2-2) EHMA, 6.2g monomer (a2-3) IBOA, 20.2g monomer (a3) N-MAM, 7.68g emulsifying agent (B-1) SP1830, 2.12g emulsifying agent (B-2) SP1807, 7.3g emulsifying agent (B-3) two ox ester group ammonium chloride (being designated as CNA-90 below), 1.2g chain-transferring agent TDM and 50g solvent DPM is oil phase, stir in 40 DEG C with homogenizer, 5g acetic acid (E) and 290g deionized water are the oil phase that aqueous phase is slowly added in high-speed stirred, stir 20 minutes after adding, uniform and stable pre-emulsion is being obtained for twice with high pressure homogenizer 40Mpa homogeneous.
Pre-emulsion is filled to the glass four-necked bottle of agitating device, erection thermometer and condensation reflux unit, vacuumize with after nitrogen replacement 2 times, continue to pass into nitrogen, be warming up to 80 DEG C, add 1.32g initiator (V-50), to trigger polymerisation, keep 10 hours in 80 DEG C, generate polymer 496.7g, solid content 29.28%.
example 5 (as shown in table 2)
35.6g monomer (a1) FA will be loaded in glass beaker, 62.3g monomer (a2-1) SA, 25.7g monomer (a2-2) EHMA, 6.2g monomer (a2-3) IBOA, 20.2g monomer (a3) N-MAM, 7.68g emulsifying agent (B-1) SP1830, 2.12g emulsifying agent (B-2) SP1807, 7.3g emulsifying agent (B-3) two fatty alkyl ethoxycarbonyl hydroxyethyl methyl sulfate methyl ammonium (being designated as WE-18 below), 1.2g chain-transferring agent TDM and 50g solvent DPM is oil phase, stir in 40 DEG C with homogenizer, 5g acetic acid (E) and 290g deionized water are the oil phase that aqueous phase is slowly added in high-speed stirred, stir 20 minutes after adding, uniform and stable pre-emulsion is being obtained for twice with high pressure homogenizer 40Mpa homogeneous.
Pre-emulsion is filled to the glass four-necked bottle of agitating device, erection thermometer and condensation reflux unit, vacuumize with after nitrogen replacement 2 times, continue to pass into nitrogen, be warming up to 80 DEG C, add 1.32g initiator (V-50), to trigger polymerisation, keep 10 hours in 80 DEG C, generate polymer 497.2g, solid content 29.46%.
Above-mentioned is preferred embodiment 1 ~ 5 of the present invention, and the difference that its composition divides is for adding different cationic emulsifier, and the fluorinated copolymer then each embodiment be polymerized measures particle diameter and current potential, and its result is as shown in table 2.
The different cationic emulsifier of interpolation of table 2 fluoropolymer
Following is present pre-ferred embodiments 6 ~ 8, and the constituent difference of its each embodiment is sentenced boldface letter and represented.
example 6 (as shown in table 3)
35.6g monomer (a1) FA will be loaded in glass beaker, 62.3g monomer (a2-1) SA, 25.7g monomer (a2-2) EHMA, 6.2g monomer (a2-3) IBOA, 20.2g monomer (a3) N-MAM, 7.68g emulsifying agent (B-1) SP1830, 2.12g emulsifying agent (B-2) SP1807, 7.3g emulsifying agent (B-3) two ox ester group ammonium chloride (CNA-90), 1.2g chain-transferring agent TDM and 50g solvent DPM is oil phase, stir in 40 DEG C with homogenizer, 3g citric acid (E) and 292g deionized water are the oil phase that aqueous phase is slowly added in high-speed stirred, stir 20 minutes after adding, uniform and stable pre-emulsion is being obtained for twice with high pressure homogenizer 40Mpa homogeneous.
Pre-emulsion is filled to the glass four-necked bottle of agitating device, erection thermometer and condensation reflux unit, vacuumize with after nitrogen replacement 2 times, continue to pass into nitrogen, be warming up to 80 DEG C, add 1.32g initiator (V-50), to trigger polymerisation, keep 10 hours in 80 DEG C, generate polymer 486.8g, solid content 29.6%.
example 7 (as shown in table 3)
35.6g monomer (a1) FA will be loaded in glass beaker, 62.3g monomer (a2-1) SA, 25.7g monomer (a2-2) EHMA, 6.2g monomer (a2-3) IBOA, 20.2g monomer (a3) N-MAM, 7.68g emulsifying agent (B-1) SP1830, 2.12g emulsifying agent (B-2) SP1807, 7.3g emulsifying agent (B-3) two ox ester group ammonium chloride (CNA-90), 1.2g chain-transferring agent TDM and 50g solvent DPM is oil phase, stir in 40 DEG C with homogenizer, 3g hydrochloric acid (E) and 292g deionized water are the oil phase that aqueous phase is slowly added in high-speed stirred, stir 20 minutes after adding, uniform and stable pre-emulsion is being obtained for twice with high pressure homogenizer 40Mpa homogeneous.
Pre-emulsion is filled to the glass four-necked bottle of agitating device, erection thermometer and condensation reflux unit, vacuumize with after nitrogen replacement 2 times, continue to pass into nitrogen, be warming up to 80 DEG C, add 1.32g initiator (V-50), to trigger polymerisation, keep 10 hours in 80 DEG C, generate polymer 486.8g, solid content 29.6%.
example 8 (as shown in table 3)
35.6g monomer (a1) FA will be loaded in glass beaker, 62.3g monomer (a2-1) SA, 25.7g monomer (a2-2) EHMA, 6.2g monomer (a2-3) IBOA, 20.2g monomer (a3) N-MAM, 7.68g emulsifying agent (B-1) SP1830, 2.12g emulsifying agent (B-2) SP1807, 7.3g emulsifying agent (B-3) two ox ester group ammonium chloride (CNA-90), 1.2g chain-transferring agent TDM and 50g solvent DPM is oil phase, stir in 40 DEG C with homogenizer, 3g phosphoric acid (E) and 292g deionized water are the oil phase that aqueous phase is slowly added in high-speed stirred, stir 20 minutes after adding, uniform and stable pre-emulsion is being obtained for twice with high pressure homogenizer 40Mpa homogeneous.
Pre-emulsion is filled to the glass four-necked bottle of agitating device, erection thermometer and condensation reflux unit, vacuumize with after nitrogen replacement 2 times, continue to pass into nitrogen, be warming up to 80 DEG C, add 1.32g initiator (V-50), to trigger polymerisation, keep 10 hours in 80 DEG C, generate polymer 486.8g, solid content 29.6%.
Above-mentioned is preferred embodiment 6 ~ 8 of the present invention, and the difference that its composition divides is for adding different acids, and the fluorinated copolymer then each embodiment be polymerized measures particle diameter and current potential, and its result is as shown in table 3.
The different acids of interpolation of table 3 fluoropolymer
The foregoing is only the better possible embodiments of the present invention, such as apply equivalent constituent and preparation method change that description of the present invention and claim do, ought to be included in right of the present invention.
Claims (8)
1. a dryingagent for fluoropolymer, includes:
(A) fluorinated copolymer, the average grain diameter in the aqueous solution is 1 ~ 1000nm, and micella current potential is 0 ~ 100mV; And
(B) cationic emulsifier of two Long carbon chain alkyl of 12 ~ 22 carbon chain lengths; And
(C) acids and its esters;
Wherein, should the cationic emulsifier of two Long carbon chain alkyl of (B) 12 ~ 22 carbon chain lengths and (C) acids and its esters be that micella control of Electric potentials in order to will be somebody's turn to do (A) fluorinated copolymer is in 0 ~ 100mV.
2. the dryingagent of fluoropolymer as claimed in claim 1, wherein, this fluoropolymer is polymerized by following monomer (a1), monomer (a2) and monomer (a3), wherein:
Monomer (al) for fluorine-containing plain monomer, its general expression be R
f-Y-X;
Wherein:
R
ffor the perfluoroalkyl of carbon number 2 ~ 20;
Y is divalent organic base or singly-bound or two isocyanide amine ester group;
X is-CR=CH
2,-C (O) OCR=CH
2,-OC (O) CR=CH
2,-OCH=CH
2,-OC
2h
4-OC (O) CR=CH
2or
r is hydrogen atom, methyl or halogen atom;
Monomer (a2) is non-fluorine element monomer, by straight chained alkyl (methyl) acrylate, branched alkyl (methyl) acrylate, and monocycle, many rings or crosslinked shape alkyl (methyl) acrylate wantonly more than two kinds of forming in group formed;
Monomer (a3) is for having the monomer of more than two reactive groups;
For this monomer (a1) 100 weight portion, this monomer (a2) is 1 ~ 300 weight portion, and this monomer (a3) is 1 ~ 50 weight portion.
3. the dryingagent of fluoropolymer as claimed in claim 1, wherein, cationic emulsifier is two octadecyl two ammonio methacrylate, two ox ester group ammonium chloride or two fatty alkyl ethoxycarbonyl hydroxyethyl methyl sulfate methyl ammoniums.
4. the dryingagent of fluoropolymer as claimed in claim 1, wherein, the better average grain diameter of this fluoropolymer is 1 ~ 200nm.
5. the dryingagent of fluoropolymer as claimed in claim 1, wherein, the better micella current potential of this fluoropolymer is 10 ~ 80mV.
6. the dryingagent of fluoropolymer as claimed in claim 1, wherein, this acids is organic acid or inorganic acid.
7. the dryingagent of fluoropolymer as claimed in claim 6, wherein, this inorganic acid is hydrochloric acid, phosphoric acid or sulfuric acid.
8. the dryingagent of fluoropolymer as claimed in claim 6, wherein, this organic acid is acetic acid or citric acid.
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| CN105019240B (en) * | 2014-04-25 | 2017-04-12 | 台氟科技股份有限公司 | Water and oil repellent agent |
| TWI642733B (en) * | 2017-09-05 | 2018-12-01 | 立得光電科技股份有限公司 | Composition of fluorine-free water repellent, fluorine-free water repellent element and fluorine-free water repellent yarn |
| CN108842469B (en) * | 2018-08-22 | 2020-09-04 | 晋江佰晟新材料科技有限公司 | Preparation method of waterproof breathable down-proof fabric |
| CN112144280A (en) * | 2019-06-27 | 2020-12-29 | 钜高新材料股份有限公司 | Fluorine-free water-based water repellent agent |
| CN115651609A (en) * | 2022-11-14 | 2023-01-31 | 天津天女化工集团股份有限公司 | Water drawing agent containing fluorine polymer |
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| CN1222929A (en) * | 1996-06-21 | 1999-07-14 | 大金工业株式会社 | Aqueous dispersion type fluorinated water- and oil-repellent |
| CN1374363A (en) * | 2001-03-05 | 2002-10-16 | 旭硝子株式会社 | Water-dispersible water-proof & oil-proof agent composition and finishing agent |
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| CN1374363A (en) * | 2001-03-05 | 2002-10-16 | 旭硝子株式会社 | Water-dispersible water-proof & oil-proof agent composition and finishing agent |
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