CN109988322A - Aqueous fluoropolymer emulsion, preparation method and application thereof - Google Patents
Aqueous fluoropolymer emulsion, preparation method and application thereof Download PDFInfo
- Publication number
- CN109988322A CN109988322A CN201910130111.7A CN201910130111A CN109988322A CN 109988322 A CN109988322 A CN 109988322A CN 201910130111 A CN201910130111 A CN 201910130111A CN 109988322 A CN109988322 A CN 109988322A
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- China
- Prior art keywords
- water
- soluble polymer
- emulsion
- optionally
- fluoropolymer
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- 239000000839 emulsion Substances 0.000 title claims abstract description 212
- 229920002313 fluoropolymer Polymers 0.000 title claims abstract description 100
- 239000004811 fluoropolymer Substances 0.000 title claims abstract description 100
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000002245 particle Substances 0.000 claims abstract description 99
- 229920003169 water-soluble polymer Polymers 0.000 claims abstract description 96
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 78
- 229920000642 polymer Polymers 0.000 claims abstract description 50
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 22
- 239000000853 adhesive Substances 0.000 claims abstract description 16
- 230000001070 adhesive effect Effects 0.000 claims abstract description 16
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 16
- 239000011737 fluorine Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims description 65
- 239000002904 solvent Substances 0.000 claims description 50
- 239000000243 solution Substances 0.000 claims description 44
- 238000003756 stirring Methods 0.000 claims description 35
- 238000011282 treatment Methods 0.000 claims description 33
- 239000011259 mixed solution Substances 0.000 claims description 28
- 238000000108 ultra-filtration Methods 0.000 claims description 28
- 238000012545 processing Methods 0.000 claims description 22
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 19
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000012752 auxiliary agent Substances 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 18
- 229920002472 Starch Polymers 0.000 claims description 15
- 239000008107 starch Substances 0.000 claims description 15
- 235000019698 starch Nutrition 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 229920001577 copolymer Polymers 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 13
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 9
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 9
- 239000008103 glucose Substances 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 229920002678 cellulose Polymers 0.000 claims description 7
- 239000001913 cellulose Substances 0.000 claims description 7
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 7
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 6
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 6
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 6
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims description 6
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims description 6
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 6
- 229920001451 polypropylene glycol Polymers 0.000 claims description 6
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 6
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 229920001897 terpolymer Polymers 0.000 claims description 5
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 125000001153 fluoro group Chemical group F* 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- VPJOGDPLXNTKAZ-UHFFFAOYSA-N 2-methylpropanoic acid;2,2,4-trimethylpentane-1,3-diol Chemical class CC(C)C(O)=O.CC(C)C(O)C(C)(C)CO VPJOGDPLXNTKAZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 2
- 239000003973 paint Substances 0.000 claims description 2
- 239000006210 lotion Substances 0.000 claims 16
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 4
- 238000012660 binary copolymerization Methods 0.000 claims 3
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 claims 3
- 230000007062 hydrolysis Effects 0.000 claims 3
- 238000006460 hydrolysis reaction Methods 0.000 claims 3
- 229940080313 sodium starch Drugs 0.000 claims 3
- 229940032147 starch Drugs 0.000 claims 3
- 229940113088 dimethylacetamide Drugs 0.000 claims 2
- CTISCMCFPOFTKK-UHFFFAOYSA-N ethene;trifluoro-$l^{3}-chlorane Chemical group C=C.FCl(F)F CTISCMCFPOFTKK-UHFFFAOYSA-N 0.000 claims 2
- ARFDIYMUJAUTDK-UHFFFAOYSA-N 1-hydroxypentyl 2-methylpropanoate Chemical compound CCCCC(O)OC(=O)C(C)C ARFDIYMUJAUTDK-UHFFFAOYSA-N 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims 1
- 239000000835 fiber Substances 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 claims 1
- 239000004005 microsphere Substances 0.000 abstract description 23
- 239000000758 substrate Substances 0.000 abstract description 23
- 238000000576 coating method Methods 0.000 abstract description 16
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 15
- 239000002002 slurry Substances 0.000 abstract description 12
- 231100000252 nontoxic Toxicity 0.000 abstract description 11
- 230000003000 nontoxic effect Effects 0.000 abstract description 11
- 238000002156 mixing Methods 0.000 description 20
- 239000003995 emulsifying agent Substances 0.000 description 19
- 230000008901 benefit Effects 0.000 description 12
- 229920000131 polyvinylidene Polymers 0.000 description 12
- 238000001338 self-assembly Methods 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 239000002033 PVDF binder Substances 0.000 description 9
- 238000010292 electrical insulation Methods 0.000 description 9
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 9
- 238000005411 Van der Waals force Methods 0.000 description 8
- 230000009881 electrostatic interaction Effects 0.000 description 8
- 230000002209 hydrophobic effect Effects 0.000 description 8
- 230000003993 interaction Effects 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 230000008961 swelling Effects 0.000 description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- 238000004945 emulsification Methods 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- IBLKWZIFZMJLFL-UHFFFAOYSA-N 1-phenoxypropan-2-ol Chemical compound CC(O)COC1=CC=CC=C1 IBLKWZIFZMJLFL-UHFFFAOYSA-N 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
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- 239000000463 material Substances 0.000 description 5
- 238000010907 mechanical stirring Methods 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000010556 emulsion polymerization method Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000009878 intermolecular interaction Effects 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 239000002671 adjuvant Substances 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000011031 large-scale manufacturing process Methods 0.000 description 3
- 231100000956 nontoxicity Toxicity 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- -1 coatings Polymers 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 206010001497 Agitation Diseases 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
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- 239000012141 concentrate Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 239000004446 fluoropolymer coating Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
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- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
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- 238000000926 separation method Methods 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
- C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
- C08J3/096—Nitrogen containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
- C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
- C08J3/097—Sulfur containing compounds
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- C09D103/02—Starch; Degradation products thereof, e.g. dextrin
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- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C09D127/16—Homopolymers or copolymers of vinylidene fluoride
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- C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
- C09D129/02—Homopolymers or copolymers of unsaturated alcohols
- C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
- C09D171/02—Polyalkylene oxides
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- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- C09J103/00—Adhesives based on starch, amylose or amylopectin or on their derivatives or degradation products
- C09J103/02—Starch; Degradation products thereof, e.g. dextrin
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C09J127/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers
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- C09J127/12—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C09J127/16—Homopolymers or copolymers of vinylidene fluoride
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- C09J129/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Adhesives based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Adhesives based on derivatives of such polymers
- C09J129/02—Homopolymers or copolymers of unsaturated alcohols
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- C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
- C09J171/02—Polyalkylene oxides
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- H—ELECTRICITY
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Abstract
本发明公开了一种乳液微粒、水性含氟聚合物乳液、制备方法及其应用。该乳液微粒包括：核心，所述核心是由含氟聚合物形成的；以及外壳，所述外壳形成于所述核心的外表面，所述核心与所述外壳通过非共价键连接，其中，所述外壳是由水溶性聚合物形成的。该乳液微粒所获得的乳液表面洁净、乳液微球的粒径单分散性好，粒径均匀、成本低廉、与多种基材具有良好的粘附性，且表面能高、表面润湿性好、不燃、无毒、环保，且在多个应用领域具有更加优异的性能，如能够用于太阳能电池背板、水性涂料、粘合剂、锂离子电池隔膜和锂离子电池电极等用的浆料组合物。The invention discloses an emulsion particle, an aqueous fluorine-containing polymer emulsion, a preparation method and an application thereof. The emulsion particles comprise: a core formed from a fluoropolymer; and a shell formed on an outer surface of the core, the core and the shell being non-covalently linked, wherein, The shell is formed from a water-soluble polymer. The emulsion particles obtained by the emulsion particles have clean surface, good particle size monodispersity of emulsion microspheres, uniform particle size, low cost, good adhesion to various substrates, high surface energy and good surface wettability , non-flammable, non-toxic, environmentally friendly, and has more excellent performance in many application fields, such as slurry that can be used in solar battery back sheets, water-based coatings, adhesives, lithium-ion battery separators and lithium-ion battery electrodes, etc. combination.
Description
技术领域technical field
本发明涉及材料领域，具体地，本发明涉及水性含氟聚合物乳液、制备方法及其应用。The present invention relates to the field of materials, in particular, the present invention relates to an aqueous fluoropolymer emulsion, a preparation method and an application thereof.
背景技术Background technique
含氟聚合物由于具有优异的化学稳定性、耐高温性、耐候性、电绝缘性以及优越的自清洁性能等功能和特点，在塑料、涂料、弹性体以及锂离子电池电极、隔膜涂层等多个领域获得了广泛应用。目前含氟聚合物涂料主要为溶剂型涂料，环境不友好。Fluoropolymers are widely used in plastics, coatings, elastomers, lithium-ion battery electrodes, separator coatings, etc. due to their excellent chemical stability, high temperature resistance, weather resistance, electrical insulation, and superior self-cleaning properties. It has been widely used in many fields. At present, fluoropolymer coatings are mainly solvent-based coatings, which are not environmentally friendly.
以含氟聚合物乳液为基础制得的环境友好型水性含氟涂料正越来越多地为人们所接受。目前水性含氟聚合物的制备工艺主要分剪切乳化法、后乳化法和乳液聚合法三类。Environmentally friendly waterborne fluorinated coatings based on fluoropolymer emulsions are increasingly accepted. At present, the preparation technology of water-based fluoropolymer is mainly divided into three categories: shear emulsification method, post-emulsification method and emulsion polymerization method.
剪切乳化法是将用其他方法制备的含氟树脂粉末、乳化剂、增稠剂和水在适当的剪切设备中高速分散形成乳液。The shear emulsification method is to disperse the fluorine-containing resin powder, emulsifier, thickener and water prepared by other methods at high speed in appropriate shearing equipment to form an emulsion.
后乳化法是在有机介质中合成水性含氟聚合物溶液，然后水性含氟聚合物溶液在乳化剂的作用下，成为分散体。The post-emulsification method is to synthesize an aqueous fluoropolymer solution in an organic medium, and then the aqueous fluoropolymer solution becomes a dispersion under the action of an emulsifier.
目前应用较多的是乳液聚合法，乳液聚合法所采用的含氟单体主要有四氟乙烯、氟乙烯、偏二氟乙烯和三氟氯乙烯四种。At present, the emulsion polymerization method is widely used. The fluorine-containing monomers used in the emulsion polymerization method mainly include tetrafluoroethylene, vinyl fluoride, vinylidene fluoride and chlorotrifluoroethylene.
剪切乳化法无论从制备过程还是产品性能来说，均不能满足现代涂料发展的需要，故现在很少使用。后乳化法存在乳液稳定性不够理想的缺点。乳液聚合条件往往需要高温高压，致使工艺复杂。The shear emulsification method cannot meet the needs of the development of modern coatings in terms of preparation process and product performance, so it is rarely used now. The post-emulsification method has the disadvantage that the stability of the emulsion is not ideal. The conditions of emulsion polymerization often require high temperature and high pressure, which makes the process complicated.
以上三种方法都需要加入乳化剂，乳化剂如果完全除去，会导致乳液破乳，稳定性遭到破坏。乳液中所含有的乳化剂进入到最终产品中会影响聚合物乳液的电性能、光学性能、表面性能、耐水性能及成膜性等，乳化剂还会造成一定的环境污染。The above three methods all need to add an emulsifier. If the emulsifier is completely removed, it will cause the emulsion to break and its stability will be destroyed. When the emulsifier contained in the emulsion enters the final product, it will affect the electrical properties, optical properties, surface properties, water resistance and film-forming properties of the polymer emulsion, and the emulsifier will also cause certain environmental pollution.
为了克服现有技术的缺陷，本领域技术人员提出了许多无乳化剂的聚合方法。In order to overcome the deficiencies of the prior art, many emulsifier-free polymerization methods have been proposed by those skilled in the art.
例如：申请号为WO9717381的专利国际申请公开了一种制备三氟氯乙烯的均聚物或共聚物的方法，它采用氧化还原体系来引发聚合反应，并且在聚合过程中，多次补加引发剂，因此它是一种无乳化剂的水乳液聚合法。但是该方法同时要求同时加入氧化剂及还原剂，这就意味着需要额外的加料路线及控制装置，而且同时加料不可避免的增加了聚合过程中失败的风险。For example: the international patent application with the application number of WO9717381 discloses a method for preparing a homopolymer or copolymer of chlorotrifluoroethylene, which uses a redox system to initiate a polymerization reaction, and during the polymerization process, multiple additional initiators are added. Therefore, it is an emulsifier-free aqueous emulsion polymerization method. However, this method requires the simultaneous addition of an oxidizing agent and a reducing agent, which means that additional feeding routes and control devices are required, and the simultaneous feeding inevitably increases the risk of failure in the polymerization process.
美国专利US2004041878开发出一种无乳化剂的氟聚合物的制备方法。该方法通过加入链转移剂来调整氟聚合物分子量并且在聚合过程中再添加氧化剂或还原剂中的一种而不是两种都加，或者添加氧化性金属离子引发聚合并在聚合过程中添加氧化性金属离子，但是该方法的缺点是引发体系中含氟烯烃的种类有所限定。US patent US2004041878 developed a preparation method of fluoropolymer without emulsifier. This method adjusts the molecular weight of the fluoropolymer by adding a chain transfer agent and adding either an oxidizing agent or a reducing agent instead of both during the polymerization process, or adding an oxidizing metal ion to initiate the polymerization and adding an oxidizing agent during the polymerization process. However, the disadvantage of this method is that the types of fluorine-containing olefins in the initiation system are limited.
因而，水性含氟聚合物乳液及其制备方法仍有待开发和改进。Thus, aqueous fluoropolymer emulsions and methods for their preparation remain to be developed and improved.
发明内容SUMMARY OF THE INVENTION
现有技术中制备水性含氟聚合物的方法中大部分需要加入乳化剂，形成的乳液中最终会包含乳化剂，而乳液中所含有的乳化剂进入到最终产品中会影响聚合物乳液的电性能、光学性能、表面性能、耐水性能及成膜性等，同时乳化剂还会造成一定的环境污染。另外虽然现有技术中会通过化学合成的方法来制备水性含氟聚合物，但面临着反应条件苛刻、所能使用的含氟烯烃的种类有限，因此，所能合成的水性含氟聚合物的种类很少。Most of the methods for preparing water-based fluoropolymers in the prior art require adding an emulsifier, and the formed emulsion will eventually contain an emulsifier, and the emulsifier contained in the emulsion enters the final product, which will affect the electrical properties of the polymer emulsion. performance, optical properties, surface properties, water resistance and film-forming properties, etc. At the same time, the emulsifier will also cause certain environmental pollution. In addition, although the water-based fluoropolymers are prepared by chemical synthesis methods in the prior art, they are faced with harsh reaction conditions and limited types of fluoroolefins that can be used. There are few kinds.
基于上述事实和问题的发现，本发明提出了一种新的乳液以及制备该乳液的方法，该乳液具有如下至少之一的优点：(1)不使用乳化剂，降低了产品成本；(2)制得的乳液表面洁净，避免了应用过程中由于乳化剂的存在对聚合物产品各种性能的不良影响；(3)制得的乳液粒子的粒径单分散性好，粒径均匀；(4)乳液表面含有大量的羟基，与多种基材具有良好的粘附性；(5)乳液制备不采用化学合成法，可以使用多种含氟聚合物，可选择的材料空间大，制备更加方便。同时该乳液解决了含氟聚合物表面能低、表面润湿性差、与其它材料的粘结性差、只能溶于溶剂等问题，并且该乳液具有无毒、无污染等环保优点，在多个应用领域具有更加优异的性能，如该乳液能够用于太阳能电池背板、水性涂料、粘合剂、锂离子电池隔膜和锂离子电池电极等的用浆料组合物，提高其粘附性、耐酸耐碱性和耐溶剂性，且制备工艺简单、操作方便，适合工业化大生产。Based on the findings of the above facts and problems, the present invention proposes a new emulsion and a method for preparing the emulsion. The emulsion has at least one of the following advantages: (1) no emulsifier is used, which reduces product cost; (2) The surface of the prepared emulsion is clean, which avoids the adverse effects on various properties of the polymer product due to the presence of the emulsifier during the application process; (3) the particle size of the prepared emulsion particles has good monodispersity and uniform particle size; (4) ) The surface of the emulsion contains a large number of hydroxyl groups, and has good adhesion to various substrates; (5) The preparation of the emulsion does not use chemical synthesis methods, and a variety of fluoropolymers can be used. The material space for selection is large, and the preparation is more convenient . At the same time, the emulsion solves the problems of low surface energy of fluoropolymer, poor surface wettability, poor adhesion with other materials, and can only be dissolved in solvents, etc., and the emulsion has environmental protection advantages such as non-toxicity and non-polluting. The application field has more excellent performance, such as the emulsion can be used in slurry compositions for solar battery back sheets, water-based coatings, adhesives, lithium ion battery separators and lithium ion battery electrodes, etc., to improve its adhesion, acid resistance, etc. Alkali resistance and solvent resistance, and the preparation process is simple, the operation is convenient, and it is suitable for industrialized large-scale production.
在本发明的第一方面，本发明提出了一种乳液微粒。根据本发明的实施例，所述乳液微粒包括：核心，所述核心是由含氟聚合物形成的；以及外壳，所述外壳形成于所述核心的外表面，所述核心与所述外壳通过非共价键连接，其中，所述外壳是由水溶性聚合物形成的。发明人巧妙地利用含氟聚合物和水溶性聚合物之间存在的分子间的作用力，如氢键、范德华力、静电作用、疏水作用等，将含氟聚合物与水溶性聚合物形成核心与外壳的微粒结构，具有这种结构的微粒在水溶液中能再次通过分子间的相互作用力，自组装成一个微球结构，最终形成一种O/W型乳液。根据本发明实施例的乳液微粒所获得的乳液表面洁净、乳液微球的粒径单分散性好，粒径均匀、成本低廉、与多种基材具有良好的粘附性，且表面能高、表面润湿性好、不燃、无毒、环保，且在多个应用领域具有更加优异的性能，如能够用于太阳能电池背板、水性涂料、粘合剂、锂离子电池隔膜和锂离子电池电极等的用浆料组合物。In a first aspect of the present invention, the present invention provides an emulsion particle. According to an embodiment of the present invention, the emulsion particles comprise: a core formed of a fluoropolymer; and a shell formed on an outer surface of the core, the core passing through the shell Non-covalently linked, wherein the shell is formed from a water soluble polymer. The inventor cleverly utilizes the intermolecular forces existing between the fluoropolymer and the water-soluble polymer, such as hydrogen bonding, van der Waals force, electrostatic interaction, hydrophobic interaction, etc., to form the core of the fluoropolymer and the water-soluble polymer With the particle structure of the shell, the particles with this structure can self-assemble into a microsphere structure through the intermolecular interaction force in the aqueous solution, and finally form an O/W type emulsion. The emulsion particles obtained by the emulsion particles according to the embodiments of the present invention have clean surface, good particle size monodispersity, uniform particle size, low cost, good adhesion to various substrates, and high surface energy, low cost, and high surface energy. Good surface wettability, non-flammable, non-toxic, environmentally friendly, and has more excellent performance in many applications, such as solar battery backsheets, water-based coatings, adhesives, lithium-ion battery separators and lithium-ion battery electrodes and other slurry compositions.
根据本发明的实施例，上述乳液微粒还可以包括如下附加技术特征至少之一：According to an embodiment of the present invention, the above-mentioned emulsion particles may further include at least one of the following additional technical features:
需要说明的是，羟基基团的个数没有特别限制，只要满足能与含氟聚合物中的F原子形成的氢键作用以及其他基团之间的静电作用、疏水作用和范德华力等非共价键作用形成乳液微粒即可。根据本发明的实施例，所述水溶性聚合物为含有羟基基团的聚合物，所述羟基基团位于所述水溶性聚合物的主链和/或支链上。根据本发明实施例的乳液微粒所获得的乳液，表面能高、表面润湿性好、与多种基材具有好的粘附性。It should be noted that the number of hydroxyl groups is not particularly limited, as long as it satisfies the hydrogen bond that can be formed with the F atom in the fluoropolymer, as well as the electrostatic interactions, hydrophobic interactions and van der Waals forces between other groups. The valence bonds can form emulsion particles. According to an embodiment of the present invention, the water-soluble polymer is a polymer containing hydroxyl groups, and the hydroxyl groups are located on the main chain and/or branch chain of the water-soluble polymer. The emulsion obtained by the emulsion particles according to the embodiment of the present invention has high surface energy, good surface wettability, and good adhesion to various substrates.
根据本发明的实施例，所述水溶性聚合物包括选自聚乙二醇、聚丙二醇、聚乙烯醇、羧甲基纤维素钠、羟甲基纤维素、纤维素、葡萄糖、淀粉以及水解淀粉钠的至少之一。发明人发现，上述水溶性聚合物所构成的乳液微粒自组装形成的乳液，表面能更高、表面润湿性更好、与多种基材具有更好的粘附性。According to an embodiment of the present invention, the water-soluble polymer is selected from the group consisting of polyethylene glycol, polypropylene glycol, polyvinyl alcohol, sodium carboxymethyl cellulose, hydroxymethyl cellulose, cellulose, glucose, starch and hydrolyzed starch at least one of sodium. The inventors found that the emulsion formed by the self-assembly of the emulsion particles composed of the above water-soluble polymer has higher surface energy, better surface wettability, and better adhesion to various substrates.
根据本发明的实施例，所述的水溶性聚合物的数均分子量为200～1000000。发明人发现，水溶性聚合物的数均分子量为200～1000000。发明人发现，如果分子量低于200，由于聚合物的分子链短，对含氟聚合物的保护性差，乳液制备的成功率会降低；如果分子量高于1000000，聚合物溶解于溶剂中时，粘度大，制备工艺不易控制，而水溶性聚合物的数均分子量在上述范围内，对含氟聚合物的保护性好，且水溶性聚合物溶解在溶剂中时，粘度适中，制备工艺容易控制，进而由数均分子量在200～1000000范围内的水溶性聚合物形成的乳液微粒自组装形成的乳液，表面能高、表面润湿性好、与多种基材具有好的粘附性。According to an embodiment of the present invention, the number average molecular weight of the water-soluble polymer is 200-1,000,000. The inventors found that the number average molecular weight of the water-soluble polymer is 200 to 1,000,000. The inventors found that if the molecular weight is lower than 200, due to the short molecular chain of the polymer, the protection of the fluoropolymer is poor, and the success rate of emulsion preparation will decrease; if the molecular weight is higher than 1,000,000, when the polymer is dissolved in the solvent, the viscosity The number-average molecular weight of the water-soluble polymer is within the above range, and the protection of the fluorine-containing polymer is good, and when the water-soluble polymer is dissolved in the solvent, the viscosity is moderate, and the preparation process is easy to control. Furthermore, an emulsion formed by self-assembly of emulsion particles formed by a water-soluble polymer with a number-average molecular weight in the range of 200-1,000,000 has high surface energy, good surface wettability, and good adhesion to various substrates.
根据本发明的实施例，所述的水溶性聚合物的数均分子量为500～500000。发明人发现，水溶性聚合物的数均分子量在上述范围内，乳液微粒自组装形成的乳液，表面能更高、表面润湿性更好、与多种基材具有更好的粘附性。According to an embodiment of the present invention, the number average molecular weight of the water-soluble polymer is 500-500,000. The inventors found that when the number average molecular weight of the water-soluble polymer is within the above range, the emulsion formed by the self-assembly of the emulsion particles has higher surface energy, better surface wettability, and better adhesion to various substrates.
根据本发明的实施例，所述的水溶性聚合物的数均分子量为2000～300000。发明人发现，水溶性聚合物的数均分子量在上述范围内，乳液微粒自组装形成的乳液，表面能更进一步提高、表面润湿性更进一步提高、与多种基材具有更进一步提高的粘附性。According to an embodiment of the present invention, the number average molecular weight of the water-soluble polymer is 2,000-300,000. The inventors found that when the number-average molecular weight of the water-soluble polymer is within the above range, the emulsion formed by the self-assembly of the emulsion particles has a further improved surface energy, a further improved surface wettability, and a further improved adhesion to various substrates. Attachment.
根据本发明的实施例，所述水溶性聚合物的用量为0.5～60重量份。发明人发现，如果水溶性聚合物的用量低于0.5重量份，聚合物乳液的效率低，如果水溶性聚合物的用量高于60重量份，所形成的聚合物的粘度较大，气泡较多，实际应用会有一些不利的影响，水溶性聚合物的用量在上述范围内，聚合物乳液的效率高，所形成的聚合物粘度适中，有利于实际应用，进而由0.5～60重量份的水溶性聚合物所形成的乳液微粒自组装形成的乳液，表面能高、表面润湿性好、与多种基材具有好的粘附性。According to an embodiment of the present invention, the water-soluble polymer is used in an amount of 0.5-60 parts by weight. The inventors found that if the amount of the water-soluble polymer is less than 0.5 parts by weight, the efficiency of the polymer emulsion is low, and if the amount of the water-soluble polymer is higher than 60 parts by weight, the viscosity of the formed polymer is high and the bubbles are more. , the practical application will have some adverse effects, the amount of water-soluble polymer is within the above range, the efficiency of the polymer emulsion is high, the viscosity of the formed polymer is moderate, which is beneficial to practical application, and then the water-soluble polymer of 0.5 to 60 parts by weight is used. The emulsion formed by the self-assembly of the emulsion particles formed by the polymer has high surface energy, good surface wettability, and good adhesion to various substrates.
根据本发明的实施例，所述水溶性聚合物的用量为1～20重量份。发明人发现，水溶性聚合物的用量在上述范围内，乳液微粒自组装形成的乳液，表面能更高、表面润湿性更好、与多种基材具有更好的粘附性。According to an embodiment of the present invention, the water-soluble polymer is used in an amount of 1-20 parts by weight. The inventors found that when the amount of the water-soluble polymer is within the above range, the emulsion formed by the self-assembly of the emulsion particles has higher surface energy, better surface wettability, and better adhesion to various substrates.
根据本发明的实施例，所述非共价键为氢键。发明人巧妙地利用含氟聚合物中的F原子与水溶性聚合物中的羟基中的H原子之间形成的氢键作用，将含氟聚合物与水溶性聚合物发生自组装成乳液微粒的核心和外壳结构。根据本发明实施例的乳液微粒结构较为稳定，粒径单分散性好，粒径均匀、成本低廉。According to an embodiment of the present invention, the non-covalent bond is a hydrogen bond. The inventor cleverly utilizes the hydrogen bond formed between the F atom in the fluoropolymer and the H atom in the hydroxyl group in the water-soluble polymer to self-assemble the fluoropolymer and the water-soluble polymer into emulsion particles. Core and shell structure. The emulsion particle structure according to the embodiment of the present invention is relatively stable, the particle size monodispersity is good, the particle size is uniform, and the cost is low.
需要说明的是，含氟聚合物的种类不受特别限制，只要含氟聚合物与水溶性化合物形成的氢键作用以及静电作用、疏水作用和范德华力等非共价键作用形成乳液微粒即可。根据本发明的实施例，所述含氟聚合物包括选自聚偏氟乙烯、偏氟乙烯、四氟乙烯、六氟丙烯、三氟氯乙烯进行聚合所获得的二元共聚体、三元共聚体以及四元共聚体中的至少之一。发明人发现，上述含氟聚合物构成的乳液微粒自组装形成的乳液，具有耐化学性、介电性能高、电气绝缘、耐高温、可焊性好、防潮性好、透明和机械强度高等优点。It should be noted that the type of fluoropolymer is not particularly limited, as long as the hydrogen bond formed by the fluoropolymer and the water-soluble compound and the non-covalent bond such as electrostatic interaction, hydrophobic interaction and van der Waals force can form emulsion particles. . According to an embodiment of the present invention, the fluorine-containing polymer includes a binary copolymer, a terpolymer selected from the group consisting of polyvinylidene fluoride, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, and chlorotrifluoroethylene obtained by polymerizing at least one of a tetramer and a quaternary copolymer. The inventor found that the emulsion formed by the self-assembly of the emulsion particles composed of the above-mentioned fluoropolymer has the advantages of chemical resistance, high dielectric properties, electrical insulation, high temperature resistance, good solderability, good moisture resistance, transparency and high mechanical strength. .
根据本发明的实施例，所述含氟聚合物的数均分子量为100000～1000000。发明人发现，当含氟聚合物的数均分子量为100000以下时，含氟聚合物的玻璃点转化温度太低，耐热性较差。当含氟聚合物的数均分子量为1000000以上时，制备水性含氟聚合物乳液的成功率低。发明人发现，含氟聚合物的数均分子量在上述范围内，乳液微粒自组装形成的乳液，具有耐化学性、介电性能高、电气绝缘、耐高温、可焊性好、防潮性好、透明和机械强度高等优点。According to an embodiment of the present invention, the number average molecular weight of the fluoropolymer is 100,000-1,000,000. The inventors found that when the number average molecular weight of the fluoropolymer is 100,000 or less, the glass point transition temperature of the fluoropolymer is too low and the heat resistance is poor. When the number average molecular weight of the fluoropolymer is 1,000,000 or more, the success rate of preparing the aqueous fluoropolymer emulsion is low. The inventors found that when the number average molecular weight of the fluoropolymer is within the above range, the emulsion formed by the self-assembly of the emulsion particles has chemical resistance, high dielectric properties, electrical insulation, high temperature resistance, good solderability, good moisture resistance, The advantages of transparency and high mechanical strength.
根据本发明的实施例，所述含氟聚合物的数均分子量为200000～800000。发明人发现，含氟聚合物的数均分子量在上述范围内，乳液微粒自组装形成的乳液，具有更耐化学性、介电性能更高、电气绝缘、更耐高温、可焊性更好、防潮性更好、透明和机械强度更高等优点。According to an embodiment of the present invention, the number average molecular weight of the fluoropolymer is 200,000-800,000. The inventors found that when the number average molecular weight of the fluoropolymer is within the above range, the emulsion formed by the self-assembly of the emulsion particles has better chemical resistance, higher dielectric properties, electrical insulation, higher temperature resistance, better solderability, The advantages of better moisture resistance, transparency and higher mechanical strength.
根据本发明的实施例，所述含氟聚合物的用量为0.5～60重量份。发明人发现，如果含氟聚合物的用量低于0.5重量份，乳液中含含氟聚合物的量低，无法发挥乳液的系列优势，如果高于60重量份，体系的粘度大，会导致制备和应用工艺难控制，含氟聚合物的用量在上述范围内，乳液微粒自组装形成的乳液，具有耐化学性、介电性能高、电气绝缘、耐高温、可焊性好、防潮性好、透明和机械强度高等优点。According to an embodiment of the present invention, the amount of the fluoropolymer used is 0.5-60 parts by weight. The inventors found that if the amount of the fluoropolymer used is less than 0.5 parts by weight, the amount of the fluoropolymer in the emulsion is low, and the series advantages of the emulsion cannot be exerted. It is difficult to control the application process and the dosage of fluoropolymers within the above range. The emulsion formed by the self-assembly of emulsion particles has chemical resistance, high dielectric properties, electrical insulation, high temperature resistance, good solderability, and moisture resistance. The advantages of transparency and high mechanical strength.
根据本发明的实施例，所述含氟聚合物的用量为0.5～10重量份。发明人发现，含氟聚合物的用量在上述范围内，乳液微粒自组装形成的乳液，具有更耐化学性、介电性能更高、电气绝缘、更耐高温、可焊性更好、防潮性更好、透明和机械强度更高等优点。According to an embodiment of the present invention, the amount of the fluoropolymer used is 0.5-10 parts by weight. The inventors found that when the amount of the fluoropolymer is within the above range, the emulsion formed by the self-assembly of the emulsion particles has better chemical resistance, higher dielectric properties, electrical insulation, higher temperature resistance, better solderability, and moisture resistance. better, transparent and mechanically stronger.
根据本发明的实施例，所述含氟聚合物和水溶性聚合物的比例为1:2～1:10，优选为1:2～1:5；如果含氟聚合物和水溶性聚合物的比例高于1:2，由于含氟聚合物的比例太高，含氟聚合物和水溶性聚合物形成的微粒亲水性基团太少，会导致制备工艺难控制；如果含氟聚合物和水溶性聚合物的比例低于1:10，无法发挥乳液的系列优势。According to an embodiment of the present invention, the ratio of the fluoropolymer to the water-soluble polymer is 1:2 to 1:10, preferably 1:2 to 1:5; If the ratio is higher than 1:2, because the ratio of the fluoropolymer is too high, the hydrophilic groups of the particles formed by the fluoropolymer and the water-soluble polymer are too small, which will lead to difficult control of the preparation process; if the fluoropolymer and The ratio of water-soluble polymer is lower than 1:10, and the series advantages of emulsion cannot be exerted.
根据本发明的实施例，所述核心进一步包括助剂。进而进一步稳定乳液微粒的结构。According to an embodiment of the present invention, the core further includes an adjuvant. This further stabilizes the structure of the emulsion particles.
根据本发明的实施例，所述助剂包括选自2，2，4-三甲基-1，3-戊二醇单异丁酸酯、苯甲醇、乙二醇丁醚以及丙二醇苯醚的至少之一。进而更进一步稳定乳液微粒的结构。According to an embodiment of the present invention, the auxiliary agent comprises a compound selected from the group consisting of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, benzyl alcohol, ethylene glycol butyl ether and propylene glycol phenyl ether. at least one. This further stabilizes the structure of the emulsion particles.
根据本发明的实施例，所述助剂的用量为0～5重量份。发明人发现，助剂在0～5重量份的用量下，能更进一步稳定乳液微粒的结构。According to an embodiment of the present invention, the amount of the auxiliary agent is 0-5 parts by weight. The inventors found that the adjuvant can further stabilize the structure of the emulsion particles when the amount of the auxiliary agent is 0-5 parts by weight.
在本发明的第二方面，本发明提出了一种乳液。根据本发明的实施例，所述乳液包括数个乳液微球，所述乳液微球是由前面所述的乳液微粒在水中聚集形成的。发明人巧妙地利用含氟聚合物和水溶性聚合物之间存在的分子间的作用力，如氢键、范德华力、静电作用、疏水作用等，将含氟聚合物与水溶性聚合物形成核心与外壳的乳液微粒结构，具有这种结构的微粒在水溶液中能再次通过分子间的相互作用力，自组装成一个微球结构，最终形成一种O/W型的上述乳液。根据本发明实施例的乳液表面洁净、乳液微球的粒径单分散性好，粒径均匀、成本低廉、与多种基材具有良好的粘附性，且表面能高、表面润湿性好、不燃、无毒、环保，且在多个应用领域具有更加优异的性能，如能够用于太阳能电池背板、水性涂料、粘合剂、锂离子电池隔膜和锂离子电池电极等的用浆料组合物。In a second aspect of the present invention, the present invention proposes an emulsion. According to an embodiment of the present invention, the emulsion includes a plurality of emulsion microspheres, and the emulsion microspheres are formed by aggregating the aforementioned emulsion particles in water. The inventor cleverly utilizes the intermolecular forces existing between the fluoropolymer and the water-soluble polymer, such as hydrogen bonding, van der Waals force, electrostatic interaction, hydrophobic interaction, etc., to form the core of the fluoropolymer and the water-soluble polymer With the emulsion particle structure of the shell, the particles with this structure can self-assemble into a microsphere structure through the intermolecular interaction force in the aqueous solution, and finally form an O/W type of the above emulsion. According to the embodiment of the present invention, the surface of the emulsion is clean, the particle size of the emulsion microspheres has good monodispersity, the particle size is uniform, the cost is low, and the emulsion has good adhesion with various substrates, and the surface energy is high and the surface wettability is good. , non-flammable, non-toxic, environmentally friendly, and has more excellent performance in many application fields, such as slurry for solar battery back sheets, water-based coatings, adhesives, lithium-ion battery separators and lithium-ion battery electrodes, etc. combination.
根据本发明的实施例，上述乳液还可以进一步包括如下所述的附加技术特征至少之一：According to an embodiment of the present invention, the above-mentioned emulsion may further include at least one of the following additional technical features:
根据本发明的实施例，所述乳液微球的平均粒径为10～1000nm。发明人发现，如果乳液微球的平均粒径小于10nm，乳液稳定性变差，容易团聚，如果平均粒径大于1000nm，用作粘合剂时涂层表面平整度和厚度不易控制，乳液微球的平均粒径在上述范围内时，乳液稳定性好，不容易团聚，且用作粘合剂时涂层表面平整度和厚度容易控制，因而更加本发明实施例的乳液中的乳液微球粒径单分散性好，粒径均匀，表面能高，表面润湿性好，且无毒、环保、成本低廉。According to an embodiment of the present invention, the average particle size of the emulsion microspheres is 10-1000 nm. The inventor found that if the average particle size of the emulsion microspheres is less than 10 nm, the stability of the emulsion becomes poor, and it is easy to agglomerate. When the average particle size is within the above range, the emulsion stability is good, it is not easy to agglomerate, and the coating surface flatness and thickness are easy to control when used as a binder, so the emulsion microspheres in the emulsion of the embodiment of the present invention are more It has good monodispersity, uniform particle size, high surface energy, good surface wettability, non-toxic, environmentally friendly and low cost.
根据本发明的实施例，所述乳液微球的平均粒径为30nm～800nm。发明人发现，乳液微球的平均粒径在上述范围内时，上述乳液中的乳液微球粒径单分散性更好，粒径更均匀，表面能更高，表面润湿性更好，且无毒、环保、成本低廉。According to an embodiment of the present invention, the average particle size of the emulsion microspheres is 30 nm to 800 nm. The inventors found that when the average particle size of the emulsion microspheres is within the above range, the emulsion microspheres in the emulsion have better particle size monodispersity, more uniform particle size, higher surface energy, and better surface wettability, and Non-toxic, environmentally friendly and low cost.
根据本发明的实施例，所述乳液微球的平均粒径为50nm～700nm。明人发现，乳液微球的平均粒径在上述范围内时，上述乳液的粒径单分散性更进一步提好，粒径均匀度更进一步提高，表面能更进一步提高，表面润湿性更进一步提高，且无毒、环保、成本低廉。According to an embodiment of the present invention, the average particle size of the emulsion microspheres is 50 nm to 700 nm. Ming people found that when the average particle size of the emulsion microspheres was within the above range, the particle size monodispersity of the above-mentioned emulsion was further improved, the particle size uniformity was further improved, the surface energy was further improved, and the surface wettability was further improved. It is non-toxic, environmentally friendly and low in cost.
根据本发明的实施例，所述乳液微粒的用量为0.5～60重量份，所述水的用量为60～99重量份。发明人发现，在乳液微粒的用量为0.5～60重量份、水的用量为60～99重量份的条件下，乳液微粒能均匀分散在水中，进而，所述乳液中的乳液微球的粒径单分散性好，粒径均匀，表面能高，表面润湿性好，且无毒、环保、成本低廉。According to an embodiment of the present invention, the dosage of the emulsion particles is 0.5-60 parts by weight, and the dosage of the water is 60-99 parts by weight. The inventor found that under the condition that the amount of emulsion particles is 0.5-60 parts by weight and the amount of water is 60-99 parts by weight, the emulsion particles can be uniformly dispersed in water, and further, the particle size of the emulsion microspheres in the emulsion Good monodispersity, uniform particle size, high surface energy, good surface wettability, non-toxic, environmentally friendly and low cost.
根据本发明的实施例，所述乳液微粒的用量为0.5～20重量份，所述水的用量为70～99重量份。发明人发现，在乳液微粒的用量为0.5～20重量份，水的用量为70～99重量份的条件下，乳液微粒能更加均匀分散在水中，进而上述乳液中的乳液微球的粒径单分散性更好，粒径更均匀，表面能更高，表面润湿性更好，且无毒、环保、成本低廉。According to an embodiment of the present invention, the dosage of the emulsion particles is 0.5-20 parts by weight, and the dosage of the water is 70-99 parts by weight. The inventors found that under the condition that the amount of emulsion particles is 0.5-20 parts by weight and the amount of water is 70-99 parts by weight, the emulsion particles can be more uniformly dispersed in water, and the particle size of the emulsion microspheres in the above emulsion is single. Better dispersibility, more uniform particle size, higher surface energy, better surface wettability, non-toxic, environmentally friendly, and low cost.
在本发明的第三方面，本发明提出了一种制备乳液的方法。根据本发明的实施例，所述方法包括：1)将水溶性聚合物与第一溶剂进行第一混合处理，以便获得水溶性聚合物溶液，2)将含氟聚合物与第二溶剂进行第二混合处理，以便获得含氟聚合物溶液，3)将所述水溶性聚合物溶液与所述含氟聚合物溶液进行第三混合处理，以便得到混合溶液，4)将所述混合溶液与水进行第四混合处理，以便获得所述乳液。需要说明的是，本发明中步骤1)和步骤2)的编号并不能对其顺序作为限定，根据本发明实施例的方法可以先进行步骤1)再进行步骤2)，也可以先进行步骤2)再进行步骤1)，还可以同时进行步骤1)和步骤2)。发明人巧妙地利用含氟聚合物和水溶性聚合物之间存在的分子间的作用力，如氢键、范德华力、静电作用、疏水作用等，将含氟聚合物与水溶性聚合物形成核心与外壳的微粒结构，具有这种结构的微粒在水溶液中能再次通过分子间的相互作用力，自组装成一个微球结构，最终形成一种O/W型乳液。根据本发明实施例的方法，不需要添加乳化剂，避免了乳化剂进入到最终产品中会影响聚合物乳液的电性能、光学性能、表面性能、耐水性能及成膜性等的缺点，并且不需要特殊的设备，只需要搅拌装置、加热装置及超滤装置就能完成，加工工艺简单、操作方便、成本合理，适合工业化大生产。且根据本发明实施例的方法制备得到的乳液表面洁净、乳液微球的粒径单分散性好，粒径均匀、成本低廉、与多种基材具有良好的粘附性，且表面能高、表面润湿性好、不燃、无毒、环保，且在多个应用领域具有更加优异的性能，如能够用于太阳能电池背板、水性涂料、粘合剂、锂离子电池隔膜和锂离子电池电极等的用浆料组合物。In the third aspect of the present invention, the present invention proposes a method for preparing an emulsion. According to an embodiment of the present invention, the method includes: 1) subjecting a water-soluble polymer to a first mixing treatment with a first solvent to obtain a water-soluble polymer solution; 2) subjecting a fluoropolymer to a second solvent for a first mixing process Second mixing treatment to obtain a fluoropolymer solution, 3) subjecting the water-soluble polymer solution and the fluoropolymer solution to a third mixing treatment to obtain a mixed solution, 4) mixing the mixed solution with water A fourth mixing process is performed in order to obtain the emulsion. It should be noted that the numbering of steps 1) and 2) in the present invention does not limit their order. According to the method of the embodiment of the present invention, step 1) may be performed first and then step 2), or step 2 may be performed first. ) and then step 1), and step 1) and step 2) can also be performed at the same time. The inventor cleverly utilizes the intermolecular forces existing between the fluoropolymer and the water-soluble polymer, such as hydrogen bonding, van der Waals force, electrostatic interaction, hydrophobic interaction, etc., to form the core of the fluoropolymer and the water-soluble polymer With the particle structure of the shell, the particles with this structure can self-assemble into a microsphere structure through the intermolecular interaction force in the aqueous solution, and finally form an O/W type emulsion. According to the method of the embodiment of the present invention, it is not necessary to add an emulsifier, which avoids the disadvantage that the emulsifier enters the final product and affects the electrical properties, optical properties, surface properties, water resistance and film-forming properties of the polymer emulsion. Special equipment is required, and only a stirring device, a heating device and an ultrafiltration device are needed to complete the process. The processing technology is simple, the operation is convenient, and the cost is reasonable, and it is suitable for industrialized large-scale production. And the emulsion prepared according to the method of the embodiment of the present invention has clean surface, good particle size monodispersity of emulsion microspheres, uniform particle size, low cost, good adhesion with various substrates, and high surface energy, Good surface wettability, non-flammable, non-toxic, environmentally friendly, and has more excellent performance in many applications, such as solar battery backsheets, water-based coatings, adhesives, lithium-ion battery separators and lithium-ion battery electrodes and other slurry compositions.
根据本发明的实施例，上述方法还可以进一步包括如下附加技术特征至少之一：According to an embodiment of the present invention, the above method may further include at least one of the following additional technical features:
根据本发明的实施例，所述第一溶剂为水和/或能够与水混溶且能够将水溶性聚合物完全溶解的有机溶剂；所述第二溶剂为能够与水混溶且能够将含氟聚合物完全溶解的有机溶剂。According to an embodiment of the present invention, the first solvent is water and/or an organic solvent that is miscible with water and can completely dissolve the water-soluble polymer; the second solvent is water-miscible and can dissolve the water-soluble polymer Organic solvents in which fluoropolymers are completely dissolved.
需要说明的是，羟基基团的个数没有特别限制，只要满足能与含氟聚合物中的F原子形成的氢键作用以及其他基团之间的静电作用、疏水作用和范德华力等非共价键作用形成乳液微粒即可。根据本发明的实施例，所述水溶性聚合物为含有羟基基团的聚合物，所述羟基基团位于所述水溶性聚合物的主链和/或支链上。根据本发明实施例的方法所获得的乳液，表面能高、表面润湿性好、与多种基材具有好的粘附性。It should be noted that the number of hydroxyl groups is not particularly limited, as long as it satisfies the hydrogen bond that can be formed with the F atom in the fluoropolymer, as well as the electrostatic interactions, hydrophobic interactions and van der Waals forces between other groups. The valence bonds can form emulsion particles. According to an embodiment of the present invention, the water-soluble polymer is a polymer containing hydroxyl groups, and the hydroxyl groups are located on the main chain and/or branch chain of the water-soluble polymer. The emulsion obtained by the method of the embodiment of the present invention has high surface energy, good surface wettability, and good adhesion to various substrates.
根据本发明的实施例，所述水溶性聚合物包括选自聚乙二醇、聚丙二醇、聚乙烯醇、羧甲基纤维素钠、羟甲基纤维素、纤维素、葡萄糖、淀粉以及水解淀粉钠的至少之一。发明人发现，上述水溶性聚合物来制备获得的乳液，表面能更高、表面润湿性更好、与多种基材具有更好的粘附性。According to an embodiment of the present invention, the water-soluble polymer is selected from the group consisting of polyethylene glycol, polypropylene glycol, polyvinyl alcohol, sodium carboxymethyl cellulose, hydroxymethyl cellulose, cellulose, glucose, starch and hydrolyzed starch at least one of sodium. The inventors found that the emulsion prepared by the above water-soluble polymer has higher surface energy, better surface wettability, and better adhesion to various substrates.
根据本发明的实施例，所述的水溶性聚合物的数均分子量为200～1000000。发明人发现，水溶性聚合物的数均分子量为200～1000000。发明人发现，如果分子量低于200，由于聚合物的分子链短，对含氟聚合物的保护性差，乳液制备的成功率会降低；如果分子量高于1000000，聚合物溶解于溶剂中时，粘度大，制备工艺不易控制，而水溶性聚合物的数均分子量在上述范围内，对含氟聚合物的保护性好，且水溶性聚合物溶解在溶剂中时，粘度适中，制备工艺容易控制，上述方法所获得的乳液，表面能高、表面润湿性好、与多种基材具有好的粘附性。According to an embodiment of the present invention, the number average molecular weight of the water-soluble polymer is 200-1,000,000. The inventors found that the number average molecular weight of the water-soluble polymer is 200 to 1,000,000. The inventors found that if the molecular weight is lower than 200, due to the short molecular chain of the polymer, the protection of the fluoropolymer is poor, and the success rate of emulsion preparation will decrease; if the molecular weight is higher than 1,000,000, when the polymer is dissolved in the solvent, the viscosity The number-average molecular weight of the water-soluble polymer is within the above range, and the protection of the fluorine-containing polymer is good, and when the water-soluble polymer is dissolved in the solvent, the viscosity is moderate, and the preparation process is easy to control. The emulsion obtained by the above method has high surface energy, good surface wettability, and good adhesion to various substrates.
根据本发明的实施例，所述的水溶性聚合物的数均分子量为500～500000。发明人发现，水溶性聚合物的数均分子量在上述范围内，上述方法所获得的乳液，表面能更高、表面润湿性更好、与多种基材具有更好的粘附性。According to an embodiment of the present invention, the number average molecular weight of the water-soluble polymer is 500-500,000. The inventors found that when the number average molecular weight of the water-soluble polymer is within the above range, the emulsion obtained by the above method has higher surface energy, better surface wettability, and better adhesion to various substrates.
根据本发明的实施例，所述的水溶性聚合物的数均分子量为2000～300000。发明人发现，水溶性聚合物的数均分子量在上述范围内，上述方法所获得的乳液，表面能更进一步提高、表面润湿性更进一步提高、与多种基材具有更进一步提高的粘附性。According to an embodiment of the present invention, the number average molecular weight of the water-soluble polymer is 2,000-300,000. The inventors found that when the number-average molecular weight of the water-soluble polymer is within the above range, the emulsion obtained by the above method has further improved surface energy, further improved surface wettability, and further improved adhesion to various substrates. sex.
根据本发明的实施例，所述水溶性聚合物的用量为0.5～60重量份。发明人发现，如果水溶性聚合物的用量低于0.5重量份，聚合物乳液的效率低，如果水溶性聚合物的用量高于60重量份，所形成的聚合物的粘度较大，气泡较多，实际应用会有一些不利的影响，而水溶性聚合物的用量在上述范围内，聚合物乳液的效率高，所形成的聚合物粘度适中，有利于实际应用，由此，根据本发明实施例的方法所获得的乳液，表面能高、表面润湿性好、与多种基材具有好的粘附性。According to an embodiment of the present invention, the water-soluble polymer is used in an amount of 0.5-60 parts by weight. The inventors found that if the amount of the water-soluble polymer is less than 0.5 parts by weight, the efficiency of the polymer emulsion is low, and if the amount of the water-soluble polymer is higher than 60 parts by weight, the viscosity of the formed polymer is high and the bubbles are more. , the practical application will have some adverse effects, and the amount of the water-soluble polymer is within the above range, the efficiency of the polymer emulsion is high, and the viscosity of the formed polymer is moderate, which is beneficial to practical application. Therefore, according to the embodiment of the present invention The emulsion obtained by the method has high surface energy, good surface wettability and good adhesion to various substrates.
根据本发明的实施例，所述水溶性聚合物的用量为0.5～20重量份。发明人发现，水溶性聚合物的用量在上述范围内，上述方法所获得的乳液，表面能更高、表面润湿性更好、与多种基材具有更好的粘附性。According to an embodiment of the present invention, the water-soluble polymer is used in an amount of 0.5 to 20 parts by weight. The inventors found that when the amount of the water-soluble polymer is within the above range, the emulsion obtained by the above method has higher surface energy, better surface wettability, and better adhesion to various substrates.
根据本发明的实施例，所述第一、第二混合处理是在温度为30～90℃、pH值为1～12，的条件下进行的。发明人发现，如果温度低于30℃、体系粘度大，不易混合均匀，如果处理温度高于90℃，会导致溶剂大量挥发，实际混合液的固含量不易精确控制，且对操作人员的健康产生不利影响，而温度在30～90℃的范围内时，体系粘度适中，混合均匀更加容易，且溶剂挥发少，实际混合液的固含量能精确控制，对操作人员的健康无不利影响。根据本发明的实施例，所述第一、第二混合处理是在温度为30～90℃、pH值为3～9，的条件下进行的。发明人发现，如果在pH值为3～9的范围内，聚合物间形成的氢键稳定，能形成稳定的聚合物乳液。According to an embodiment of the present invention, the first and second mixing treatments are performed under the conditions of a temperature of 30-90° C. and a pH of 1-12. The inventors found that if the temperature is lower than 30°C and the viscosity of the system is high, it is not easy to mix evenly, and if the processing temperature is higher than 90°C, a large amount of solvent will be volatilized, the solid content of the actual mixed solution is not easy to be accurately controlled, and the health of the operators will be affected. When the temperature is in the range of 30~90℃, the viscosity of the system is moderate, the mixing is easier, and the solvent is less volatile, and the solid content of the actual mixed liquid can be accurately controlled, which has no adverse effect on the health of operators. According to an embodiment of the present invention, the first and second mixing treatments are performed under the conditions of a temperature of 30-90° C. and a pH of 3-9. The inventors found that if the pH value is in the range of 3 to 9, the hydrogen bonds formed between the polymers are stable, and a stable polymer emulsion can be formed.
根据本发明的实施例，所述第三混合处理的时间至少为20min。发明人发现，至少20min能保证含氟聚合物溶液与水溶性聚合物混合均匀，进而使得含氟聚合物与水溶性聚合物在非共价键(如氢键)的作用下聚集成具有核心和外壳的结构的乳液微粒，分散在溶液中。According to an embodiment of the present invention, the time of the third mixing treatment is at least 20 minutes. The inventors found that at least 20 minutes can ensure that the fluoropolymer solution and the water-soluble polymer are uniformly mixed, so that the fluoropolymer and the water-soluble polymer aggregate into a core and a water-soluble polymer under the action of non-covalent bonds (such as hydrogen bonds). Shell structured emulsion particles, dispersed in solution.
根据本发明的实施例，所述第四混合处理是通过如下方式进行的：将所述混合溶液以0.1g/min～50g/min的速度加入水中同时进行对形成的混合液进行搅拌处理1～500min，优选为10～100min，更优选为30～60min，所述搅拌处理是在10～5000rmp优选为500～5000rmp，更优选为1000～5000rmp速度下进行的，将搅拌处理后的混合液进行超滤处理，以便除去所述第一溶剂和所述第二溶剂；将超滤处理后混合液进行超滤浓缩处理，以便获得所述乳液。需要说明的是上述混合溶液即前面所述的乳液微粒。乳液微粒在水中在分子间的作用的条件下能自组装成均匀分散的乳液微球，形成O/W型的乳液。发明人发现，如果混合液加入速度大于50g/min，会导致所制备乳液粒径不均匀，分散性变差。进而，上述混合溶液以上述速度加入水中，并以上述搅拌速度处理上述搅拌时间所获得的乳液中的乳液微粒单分散性更好、粒径更加均匀。According to an embodiment of the present invention, the fourth mixing treatment is carried out in the following manner: adding the mixed solution into water at a speed of 0.1 g/min to 50 g/min and simultaneously performing agitation treatment on the formed mixed solution for 1 to 100 g/min. 500min, preferably 10-100min, more preferably 30-60min, the stirring treatment is carried out at a speed of 10-5000rmp, preferably 500-5000rmp, more preferably 1000-5000rmp, and the mixed solution after the stirring treatment is subjected to superheating. Filtration treatment to remove the first solvent and the second solvent; ultrafiltration and concentration treatment of the mixed solution after the ultrafiltration treatment to obtain the emulsion. It should be noted that the above-mentioned mixed solution is the aforementioned emulsion microparticles. Emulsion particles can self-assemble into uniformly dispersed emulsion microspheres under the condition of intermolecular action in water to form an O/W type emulsion. The inventors found that if the addition rate of the mixed solution is greater than 50 g/min, the particle size of the prepared emulsion will be uneven and the dispersibility will be deteriorated. Furthermore, the above-mentioned mixed solution is added to water at the above-mentioned speed, and the emulsion particles in the emulsion obtained by the above-mentioned stirring speed for the above-mentioned stirring time have better monodispersity and more uniform particle size.
根据本发明的实施例，所述乳液的固含量为1～50％。发明人发现，如果乳液的固含量低于1％，含水量高，实际应用中影响干燥效率。如果乳液的固含量高于50％，乳液制备难度增加，乳液存放稳定性变差。乳液固含量在上述范围内，含水量适中，实际应用中干燥效率高，且制备简单，根据本发明的实施例制备获得的乳液稳定性提高、生产效率高、运输成本低、干燥快、能耗低等优点。According to an embodiment of the present invention, the solid content of the emulsion is 1-50%. The inventors found that if the solid content of the emulsion is lower than 1%, the water content is high, which affects the drying efficiency in practical applications. If the solid content of the emulsion is higher than 50%, the difficulty of preparation of the emulsion increases, and the storage stability of the emulsion deteriorates. The solid content of the emulsion is within the above range, the water content is moderate, the drying efficiency is high in practical application, and the preparation is simple, and the emulsion prepared according to the embodiment of the present invention has improved stability, high production efficiency, low transportation cost, fast drying, and energy consumption. inferior advantages.
根据本发明的实施例，所述混合溶液包括油相和水相，所述油相浓度为0.1％(g/g)～30％(g/g)。发明人发现，如果油相浓度低于0.1％，所制备乳液浓度低，不利于实际应用，如果油相浓度高于30％，所制备乳液的粒径不均匀，存放稳定性差，而油相浓度在上述范围内，油相能稳定地分散在水相中，所制备得到的乳液浓度适中，粒径均匀，存放稳定性好。According to an embodiment of the present invention, the mixed solution includes an oil phase and a water phase, and the concentration of the oil phase ranges from 0.1% (g/g) to 30% (g/g). The inventors found that if the oil phase concentration is lower than 0.1%, the prepared emulsion has a low concentration, which is unfavorable for practical application. Within the above range, the oil phase can be stably dispersed in the water phase, and the prepared emulsion has moderate concentration, uniform particle size and good storage stability.
根据本发明的实施例，所述混合溶液包括油相和水相，所述油相浓度为0.5％～20％。发明人发现，油相浓度在上述范围内，油相能更稳定地分散在水相中，所制备得到的乳液浓度更适中，粒径更均匀，存放稳定性更好。According to an embodiment of the present invention, the mixed solution includes an oil phase and a water phase, and the concentration of the oil phase is 0.5% to 20%. The inventors found that when the oil phase concentration is within the above range, the oil phase can be more stably dispersed in the water phase, the prepared emulsion has more moderate concentration, more uniform particle size and better storage stability.
根据本发明的实施例，所述混合溶液包括油相和水相，所述油相浓度为1％～10％。发明人发现，油相浓度在上述范围内，油相能更进一步稳定地分散在水相中，所制备得到的乳液浓度更适中，粒径更均匀，存放稳定性更优。According to an embodiment of the present invention, the mixed solution includes an oil phase and a water phase, and the concentration of the oil phase is 1% to 10%. The inventors found that when the oil phase concentration is within the above range, the oil phase can be further stably dispersed in the water phase, and the prepared emulsion has more moderate concentration, more uniform particle size and better storage stability.
根据本发明的实施例，所述第一溶剂和第二溶剂的总质量与所述水的质量比为1:1～1:100。发明人发现，如果质量比大于1:1，形成均匀乳液较为困难，如果质量比小于1:100，所制备乳液的固含量低，会导致后处理工艺比较复杂。而第一溶剂和第二溶剂的总质量与水的质量比在1:1～1:100的范围内，会比较容易形成均匀的乳液，并且所制备获得的乳液固含量适中，后处理工艺较为简单。According to an embodiment of the present invention, the mass ratio of the total mass of the first solvent and the second solvent to the water is 1:1 to 1:100. The inventor found that if the mass ratio is greater than 1:1, it is difficult to form a uniform emulsion, and if the mass ratio is less than 1:100, the solid content of the prepared emulsion is low, which will lead to complicated post-treatment processes. And the mass ratio of the total mass of the first solvent and the second solvent to the water is in the range of 1:1 to 1:100, it is easier to form a uniform emulsion, and the prepared emulsion has a moderate solid content, and the post-treatment process is relatively Simple.
根据本发明的实施例，所述第一溶剂和第二溶剂的总质量与所述水的质量之比为1:2～1:10。发明人发现，第一溶剂和第二溶剂的总质量与水的质量比在1:2～1:10的范围内，会更容易形成均匀的乳液，并且所制备获得的乳液固含量更适中，后处理工艺更简单。According to an embodiment of the present invention, the ratio of the total mass of the first solvent and the second solvent to the mass of the water is 1:2˜1:10. The inventors found that when the mass ratio of the total mass of the first solvent and the second solvent to the water is in the range of 1:2 to 1:10, it is easier to form a uniform emulsion, and the prepared emulsion has a more moderate solid content, The post-processing process is simpler.
根据本发明的实施例，所述有机溶剂包括选自四氢呋喃、二甲基乙酰胺、二甲基甲酰胺、二甲基亚砜、N-甲基吡咯烷酮、乙醇、异丙醇以及丁醇的至少之一。上述有机溶剂能与水混溶，且对于含氟聚合物和/或水溶性聚合物的溶解性好。According to an embodiment of the present invention, the organic solvent comprises at least one selected from the group consisting of tetrahydrofuran, dimethylacetamide, dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, ethanol, isopropanol and butanol one. The above-mentioned organic solvents are miscible with water and have good solubility for fluoropolymers and/or water-soluble polymers.
需要说明的是，含氟聚合物的种类不受特别限制，只要含氟聚合物与水溶性化合物形成的氢键作用以及静电作用、疏水作用和范德华力等非共价键作用形成乳液微粒即可。根据本发明的实施例，所述含氟聚合物包括选自聚偏氟乙烯、偏氟乙烯、四氟乙烯、六氟丙烯、三氟氯乙烯进行聚合所获得的二元共聚体、三元共聚体以及四元共聚体中的至少之一。发明人发现，利于上述含氟聚合物的方法制备获得的乳液具有耐化学性、介电性能高、电气绝缘、耐高温、可焊性好、防潮性好、透明和机械强度高等优点。It should be noted that the type of fluoropolymer is not particularly limited, as long as the hydrogen bond formed by the fluoropolymer and the water-soluble compound and the non-covalent bond such as electrostatic interaction, hydrophobic interaction and van der Waals force can form emulsion particles. . According to an embodiment of the present invention, the fluorine-containing polymer includes a binary copolymer, a terpolymer selected from the group consisting of polyvinylidene fluoride, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, and chlorotrifluoroethylene obtained by polymerizing at least one of a tetramer and a quaternary copolymer. The inventors found that the emulsion prepared by the above-mentioned fluoropolymer method has the advantages of chemical resistance, high dielectric properties, electrical insulation, high temperature resistance, good solderability, good moisture resistance, transparency and high mechanical strength.
根据本发明的实施例，所述含氟聚合物的数均分子量为100000～1000000。发明人发现，当含氟聚合物的数均分子量为100000以下时，含氟聚合物的玻璃点转化温度太低，耐热性较差。当含氟聚合物的数均分子量为1000000以上时，利用根据本发明实施例的方法很难成功制备水性含氟聚合物乳液。进而，利于数均分子量在上述范围内的含氟聚合物的方法所获得的乳液具有耐化学性、介电性能高、电气绝缘、耐高温、可焊性好、防潮性好、透明和机械强度高等优点。According to an embodiment of the present invention, the number average molecular weight of the fluoropolymer is 100,000-1,000,000. The inventors found that when the number average molecular weight of the fluoropolymer is 100,000 or less, the glass point transition temperature of the fluoropolymer is too low and the heat resistance is poor. When the number average molecular weight of the fluoropolymer is above 1,000,000, it is difficult to successfully prepare an aqueous fluoropolymer emulsion using the method according to the embodiment of the present invention. Furthermore, the emulsions obtained by the method favoring fluoropolymers having a number average molecular weight in the above range have chemical resistance, high dielectric properties, electrical insulation, high temperature resistance, good solderability, good moisture resistance, transparency and mechanical strength high advantage.
根据本发明的实施例，所述含氟聚合物的数均分子量为200000～800000。进而，利于数均分子量在上述范围内的含氟聚合物的方法所获得的乳液具有更耐化学性、介电性能更高、电气绝缘、更耐高温、可焊性更好、防潮性更好、透明和机械强度更高等优点。According to an embodiment of the present invention, the number average molecular weight of the fluoropolymer is 200,000-800,000. Furthermore, the emulsions obtained by the method favoring fluoropolymers having a number average molecular weight in the above-mentioned range have higher chemical resistance, higher dielectric properties, electrical insulation, higher temperature resistance, better solderability, and better moisture resistance , transparency and higher mechanical strength.
根据本发明的实施例，所述第二混合处理进一步包括加入助剂。助剂能进一步稳定乳液的结构。According to an embodiment of the present invention, the second mixing process further includes adding an auxiliary agent. Additives can further stabilize the structure of the emulsion.
根据本发明的实施例，所述助剂包括选自2，2，4-三甲基-1，3-戊二醇单异丁酸酯、苯甲醇、乙二醇丁醚以及丙二醇苯醚的至少之一。上述助剂能更进一步稳定乳液的结构。According to an embodiment of the present invention, the auxiliary agent comprises a compound selected from the group consisting of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, benzyl alcohol, ethylene glycol butyl ether and propylene glycol phenyl ether. at least one. The above additives can further stabilize the structure of the emulsion.
根据本发明的实施例，所述助剂的用量为0～5重量份。发明人发现，助剂在0～5重量份的用量下，能更进一步稳定乳液的结构。According to an embodiment of the present invention, the amount of the auxiliary agent is 0-5 parts by weight. The inventors found that the adjuvant can further stabilize the structure of the emulsion under the dosage of 0-5 parts by weight.
在本发明的第四方面，本发明提出了一种制备乳液的方法。根据本发明的实施例，所述方法包括：1)将水溶性聚合物与第一溶剂进行第一混合处理，以便获得水溶性聚合物溶液，所述第一混合处理是在温度为30～90℃、pH值为3～9的条件下进行的，所述水溶性聚合物为含有羟基基团的聚合物；所述羟基基团位于所述水溶性聚合物的主链和/或支链上，所述水溶性聚合物包括选自聚乙二醇、聚丙二醇、聚乙烯醇、羧甲基纤维素钠、羟甲基纤维素、纤维素、葡萄糖、淀粉以及水解淀粉钠的至少之一，所述的水溶性聚合物的数均分子量为2000～300000，所述水溶性聚合物的用量为0.5～20重量份，2)将含氟聚合物和/助剂与第二溶剂进行第二混合处理，以便获得含氟聚合物溶液，所述第二混合处理是在温度为30～90℃、pH值为3～9的条件下进行的，所述含氟聚合物包括选自聚偏氟乙烯、偏氟乙烯、四氟乙烯、六氟丙烯、三氟氯乙烯进行聚合所获得的二元共聚体、三元共聚体以及四元共聚体中的至少之一，所述含氟聚合物的数均分子量为200000～800000，所述含氟聚合物的用量为0.5～20重量份，所述助剂包括选自2，2，4-三甲基-1，3-戊二醇单异丁酸酯、苯甲醇、乙二醇丁醚以及丙二醇苯醚的至少之一，所述助剂的用量为0～5重量份，3)将所述水溶性聚合物溶液与所述含氟聚合物溶液进行第三混合处理，以便得到混合溶液，所述第三混合处理的时间至少为20min，所述混合溶液包括油相和水相，所述油相浓度为5％～10％，4)将所述混合溶液与水进行第四混合处理，以便获得所述乳液，所述第四混合处理是通过如下方式进行的：将所述混合溶液以0.1g/min～50g/min的速度加入水中同时进行对形成的混合液进行搅拌处理30～60min，所述搅拌处理是在1000～5000rmp的速度下进行的，将搅拌处理后的混合液进行超滤处理，以便除去所述第一溶剂和所述第二溶剂；将超滤处理后混合液进行超滤浓缩处理至固含量为1～50％，以便获得所述乳液，其中，所述第一溶剂为水和/或能够与水混溶且能够将水溶性聚合物完全溶解的有机溶剂；所述第二溶剂为能够与水混溶且能够将含氟聚合物完全溶解的有机溶剂，所述有机溶剂包括选自四氢呋喃、二甲基乙酰胺、二甲基甲酰胺、二甲基亚砜、N-甲基吡咯烷酮、乙醇、异丙醇以及丁醇的至少之一，所述第一溶剂和第二溶剂的总质量与所述水的质量比为1:2～1:10。需要说明的是，本发明中步骤1)和步骤2)的编号并不能对其顺序作为限定，根据本发明实施例的方法可以先进行步骤1)再进行步骤2)，也可以先进行步骤2)再进行步骤1)，还可以同时进行步骤1)和步骤2)。发明人巧妙地利用含氟聚合物和水溶性聚合物之间存在的分子间的作用力，如氢键、范德华力、静电作用、疏水作用等，将含氟聚合物与水溶性聚合物形成核心与外壳的微粒结构，具有这种结构的微粒在水溶液中能再次通过分子间的相互作用力，自组装成一个微球结构，最终形成一种O/W型乳液。根据本发明实施例的方法，不需要添加乳化剂，避免了乳化剂进入到最终产品中会影响聚合物乳液的电性能、光学性能、表面性能、耐水性能及成膜性等的缺点，并且不需要特殊的设备，只需要搅拌装置、加热装置及超滤装置就能完成，加工工艺简单、操作方便、成本合理，适合工业化大生产。且根据本发明实施例的方法制备得到的乳液表面洁净、乳液微球的粒径单分散性好，粒径均匀、成本低廉、与多种基材具有良好的粘附性，且表面能高、表面润湿性好、不燃、无毒、环保，且在多个应用领域具有更加优异的性能，如能够用于太阳能电池背板、水性涂料、粘合剂、锂离子电池隔膜和锂离子电池电极等的用浆料组合物。In the fourth aspect of the present invention, the present invention provides a method for preparing an emulsion. According to an embodiment of the present invention, the method includes: 1) performing a first mixing treatment on a water-soluble polymer and a first solvent to obtain a water-soluble polymer solution, and the first mixing treatment is performed at a temperature of 30-90 ℃ and pH value of 3 to 9, the water-soluble polymer is a polymer containing hydroxyl groups; the hydroxyl groups are located on the main chain and/or branch chain of the water-soluble polymer , the water-soluble polymer comprises at least one selected from polyethylene glycol, polypropylene glycol, polyvinyl alcohol, sodium carboxymethyl cellulose, hydroxymethyl cellulose, cellulose, glucose, starch and sodium hydrolyzed starch, The number average molecular weight of the water-soluble polymer is 2,000-300,000, and the amount of the water-soluble polymer is 0.5-20 parts by weight. 2) The second mixing of the fluoropolymer and/or the auxiliary agent and the second solvent is carried out. treatment to obtain a fluoropolymer solution, the second mixing treatment is carried out at a temperature of 30 to 90° C. and a pH of 3 to 9, and the fluoropolymer comprises polyvinylidene fluoride selected from the group consisting of polyvinylidene fluoride. , at least one of the binary interpolymers, ternary interpolymers and quaternary interpolymers obtained by polymerizing vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene and chlorotrifluoroethylene, the number of the fluorine-containing polymer The average molecular weight is 200,000-800,000, the amount of the fluorine-containing polymer is 0.5-20 parts by weight, and the auxiliary agent includes 2,2,4-trimethyl-1,3-pentanediol monoisobutyric acid At least one of ester, benzyl alcohol, ethylene glycol butyl ether and propylene glycol phenyl ether, the amount of the auxiliary agent is 0 to 5 parts by weight, 3) The water-soluble polymer solution and the fluorine-containing polymer solution are mixed Carry out a third mixing treatment to obtain a mixed solution, the time of the third mixing treatment is at least 20min, the mixed solution includes an oil phase and a water phase, and the concentration of the oil phase is 5% to 10%. The mixed solution is subjected to a fourth mixing treatment with water to obtain the emulsion, and the fourth mixing treatment is carried out by adding the mixed solution into water at a speed of 0.1 g/min to 50 g/min while simultaneously carrying out The formed mixed solution is subjected to stirring treatment for 30 to 60 minutes, and the stirring treatment is carried out at a speed of 1000 to 5000 rmp, and the mixed solution after the stirring treatment is subjected to ultrafiltration treatment to remove the first solvent and the first solvent. Two solvents; the mixed solution after the ultrafiltration treatment is subjected to ultrafiltration and concentration treatment to a solid content of 1-50%, so as to obtain the emulsion, wherein the first solvent is water and/or can be miscible with water and can an organic solvent that completely dissolves the water-soluble polymer; the second solvent is an organic solvent that can be miscible with water and can completely dissolve the fluorine-containing polymer, and the organic solvent includes a solvent selected from the group consisting of tetrahydrofuran, dimethylacetamide, dimethy At least one of methylformamide, dimethyl sulfoxide, N-methylpyrrolidone, ethanol, isopropanol and butanol, and the mass ratio of the total mass of the first solvent and the second solvent to the water is 1:2～1:10. It should be noted that the numbering of steps 1) and 2) in the present invention does not limit their order. According to the method of the embodiment of the present invention, step 1) may be performed first and then step 2), or step 2 may be performed first. ) and then step 1), and step 1) and step 2) can also be performed at the same time. The inventor cleverly utilizes the intermolecular forces existing between the fluoropolymer and the water-soluble polymer, such as hydrogen bonding, van der Waals force, electrostatic interaction, hydrophobic interaction, etc., to form the core of the fluoropolymer and the water-soluble polymer With the particle structure of the shell, the particles with this structure can self-assemble into a microsphere structure through the intermolecular interaction force in the aqueous solution, and finally form an O/W type emulsion. According to the method of the embodiment of the present invention, it is not necessary to add an emulsifier, which avoids the disadvantage that the emulsifier enters the final product and affects the electrical properties, optical properties, surface properties, water resistance and film-forming properties of the polymer emulsion. Special equipment is required, and only a stirring device, a heating device and an ultrafiltration device are needed to complete the process. The processing technology is simple, the operation is convenient, and the cost is reasonable, and it is suitable for industrialized large-scale production. And the emulsion prepared according to the method of the embodiment of the present invention has clean surface, good particle size monodispersity of emulsion microspheres, uniform particle size, low cost, good adhesion with various substrates, and high surface energy, Good surface wettability, non-flammable, non-toxic, environmentally friendly, and has more excellent performance in many applications, such as solar battery backsheets, water-based coatings, adhesives, lithium-ion battery separators and lithium-ion battery electrodes and other slurry compositions.
在本发明的第五方面，本发明提出了一种乳液。根据本发明的实施例，所述乳液是通过前面所述的方法获得的。根据本发明实施例的乳液表面洁净、乳液微球的粒径单分散性好，粒径均匀、成本低廉、与多种基材具有良好的粘附性，且表面能高、表面润湿性好、不燃、无毒、环保，且在多个应用领域具有更加优异的性能，如能够用于太阳能电池背板、水性涂料、粘合剂、锂离子电池隔膜和锂离子电池电极等的用浆料组合物。In a fifth aspect of the present invention, the present invention provides an emulsion. According to an embodiment of the present invention, the emulsion is obtained by the method described above. According to the embodiment of the present invention, the surface of the emulsion is clean, the particle size of the emulsion microspheres has good monodispersity, the particle size is uniform, the cost is low, and the emulsion has good adhesion with various substrates, and the surface energy is high and the surface wettability is good. , non-flammable, non-toxic, environmentally friendly, and has more excellent performance in many application fields, such as slurry for solar battery back sheets, water-based coatings, adhesives, lithium-ion battery separators and lithium-ion battery electrodes, etc. combination.
在本发明的第六方面，本发明提出了一种太阳能电池背板粘合剂。根据本发明的实施例，所述粘合剂包括前面所述的乳液或根据前面所述的方法获得的乳液。发明人发现，保护前面所述的乳液的粘合剂可用于粘结PET层和聚烯烃层以及粘结聚烯烃层和含氟层，根据本发明实施例的太阳能电池背板粘合剂具有优良的粘结性，耐湿热型和耐候性。In a sixth aspect of the present invention, the present invention provides a solar cell back sheet adhesive. According to an embodiment of the present invention, the adhesive comprises the aforementioned emulsion or an emulsion obtained according to the aforementioned method. The inventors found that the adhesive protecting the aforementioned emulsion can be used to bond the PET layer and the polyolefin layer as well as the polyolefin layer and the fluorine-containing layer, and the solar cell back sheet adhesive according to the embodiment of the present invention has excellent Excellent adhesion, heat and humidity resistance and weather resistance.
在本发明的第七方面，本发明提出了前面所述的乳液在制备用浆组合物中的用途。根据本发明的实施例，所述乳液表面洁净、乳液微球的粒径单分散性好，粒径均匀、成本低廉、与多种基材具有良好的粘附性，且表面能高、表面润湿性好、不燃、无毒、环保，能有效用于用浆组合物的应用中。In a seventh aspect of the present invention, the present invention proposes the use of the aforementioned emulsion in the preparation of a slurry composition. According to the embodiments of the present invention, the emulsion surface is clean, the particle size of the emulsion microspheres has good monodispersity, uniform particle size, low cost, good adhesion to various substrates, and has high surface energy and surface moisturization. It has good wettability, non-flammability, non-toxicity and environmental protection, and can be effectively used in the application of pulp composition.
根据本发明的实施例，所述用浆料组合物包括选自太阳能电池背板、水性涂料、粘合剂、锂离子电池隔膜以及锂离子电池电极用浆料组合物的至少之一。根据本发明的实施例，在太阳能电池背板、水性涂料、粘合剂、锂离子电池隔膜以及锂离子电池电极的用浆料组合物中的性能更优。According to an embodiment of the present invention, the slurry composition for use includes at least one selected from the group consisting of solar battery back sheets, water-based coatings, adhesives, lithium ion battery separators and slurry compositions for lithium ion battery electrodes. According to the embodiments of the present invention, the performance is better in the slurry composition for solar battery back sheets, water-based coatings, adhesives, lithium ion battery separators and lithium ion battery electrodes.
根据本发明的实施例，本发明与现有技术相比具有如下至少之一的有益效果：According to the embodiment of the present invention, the present invention has at least one of the following beneficial effects compared with the prior art:
1)本发明中的含氟聚合物乳液，主要通过含氟聚合物和含羟基的水溶性聚合物之间形成分子间氢键的作用，形成两亲聚合物，两亲性聚合物由于同时含有化学性质不同的链段,易发生微相分离,在乳液制备过程中不用加入乳化剂，避免了乳化剂进入到最终产品中会影响聚合物乳液的电性能、光学性能、表面性能、耐水性能及成膜性等的缺陷。1) The fluoropolymer emulsion in the present invention forms an amphiphilic polymer mainly through the formation of intermolecular hydrogen bonds between the fluoropolymer and the hydroxyl-containing water-soluble polymer. Chain segments with different chemical properties are prone to microphase separation. No emulsifier is added during the preparation of the emulsion, so that the entry of the emulsifier into the final product will affect the electrical properties, optical properties, surface properties, water resistance and other properties of the polymer emulsion. Defects such as film formation.
2)本发明的含氟聚合物乳液制备过程中，不需要特殊的设备，只需要搅拌装置、加热装置及超滤装置就能完成，加工工艺简单、操作方便、成本合理。2) In the preparation process of the fluorine-containing polymer emulsion of the present invention, no special equipment is required, and only a stirring device, a heating device and an ultrafiltration device are needed to complete the process, and the processing technology is simple, the operation is convenient, and the cost is reasonable.
3)本发明的含氟聚合物乳液由于引入了含羟基的水溶性聚合物，聚合物表面含有大量的羟基，由于羟基的作用能够与多种基材具有良好的粘附性。3) The fluoropolymer emulsion of the present invention contains a large number of hydroxyl groups on the surface of the polymer due to the introduction of a hydroxyl group-containing water-soluble polymer, and can have good adhesion with various substrates due to the function of the hydroxyl groups.
4)本发明公开的含氟聚合物乳液能够用于太阳能电池背板、水性涂料、粘合剂、锂离子电池隔膜或锂离子电池电极用浆料组合物，提高其耐酸耐碱性和耐溶剂性，且本发明公开的水性含氟聚合物乳液具有不燃、无毒、无污染等环保优点。4) The fluorine-containing polymer emulsion disclosed in the present invention can be used in solar battery back sheets, water-based paints, adhesives, lithium ion battery separators or slurry compositions for lithium ion battery electrodes to improve its acid and alkali resistance and solvent resistance. The water-based fluoropolymer emulsion disclosed in the present invention has environmental protection advantages such as non-flammability, non-toxicity and non-polluting.
具体实施方式Detailed ways
如无特别说明，本申请所述的“数均分子量”是指聚合物是由化学组成相同而聚合度不等的同系混合物组成的，即由分子链长度不同的高聚物混合组成。通常采用平均数分子量表征分子的大小。按分子数目统计平均，则称为数均分子量，符号为(MN)。Unless otherwise specified, the "number average molecular weight" mentioned in this application means that the polymer is composed of a homologous mixture with the same chemical composition but different degrees of polymerization, that is, a mixture of high polymers with different molecular chain lengths. The average molecular weight is usually used to characterize the size of the molecule. According to the statistical average of the number of molecules, it is called the number-average molecular weight, and the symbol is (MN).
如无特别说明，本申请所述的“固含量”是指乳液或涂料在规定条件下烘干后剩余部分占总量的质量百分数。Unless otherwise specified, the "solid content" mentioned in this application refers to the mass percentage of the total amount of the remaining part of the emulsion or coating after drying under specified conditions.
下面详细描述本发明的实施例。下面通过描述的实施例是示例性的，旨在用于解释本发明，而不能理解为对本发明的限制。Embodiments of the present invention are described in detail below. The embodiments described below are exemplary, and are intended to be used to explain the present invention, but should not be construed as a limitation of the present invention.
实施例1Example 1
水性含氟聚合物乳液的制备步骤：Preparation steps of aqueous fluoropolymer emulsion:
(1)在1000rpm的搅拌状态下，将2g数均分子量约为100，000的聚乙烯醇缓慢加入到98g二甲基乙酰胺中，溶胀1小时后，升温至65℃，溶解完全，得到聚乙烯醇溶液。(1) under the stirring state of 1000rpm, slowly add 2g of polyvinyl alcohol with a number average molecular weight of about 100,000 to 98g of dimethylacetamide, swell for 1 hour, heat up to 65°C, dissolve completely, and obtain a polymer Vinyl alcohol solution.
(2)在1000rpm的搅拌状态下，将1g数均分子量约为600，000的聚偏氟乙烯缓慢加入到20g二甲基乙酰胺中，溶胀1小时后，升温至65℃，溶解完全，再加入得到聚偏氟乙烯溶液。(2) Under the stirring state of 1000rpm, 1g of polyvinylidene fluoride with a number average molecular weight of about 600,000 was slowly added to 20g of dimethylacetamide. Add to obtain a polyvinylidene fluoride solution.
(3)在700rpm的搅拌条件下，将聚偏氟乙烯溶液与聚乙烯醇溶液混合均匀，形成油相，油相浓度为2.48％。(3) Under the stirring condition of 700 rpm, the polyvinylidene fluoride solution and the polyvinyl alcohol solution are mixed uniformly to form an oil phase, and the oil phase concentration is 2.48%.
(4)在1000rpm的搅拌条件下，以1g/min的速度将油相慢速滴加到500ml水中，滴加完毕再搅拌30min，制得聚乙烯醇-聚偏氟乙烯初级乳液，超滤除去二甲基乙酰胺，继续超滤浓缩至固含量为10％时，停止超滤，形成聚乙烯醇-聚偏氟乙烯乳液。所形成乳液的平均粒径为548nm。(4) Under the stirring condition of 1000rpm, the oil phase was slowly added dropwise to 500ml of water at a speed of 1g/min, and then stirred for 30min after the dropwise addition to obtain a polyvinyl alcohol-polyvinylidene fluoride primary emulsion, which was removed by ultrafiltration Dimethylacetamide, continue to ultrafiltration and concentrate until the solid content is 10%, stop ultrafiltration to form a polyvinyl alcohol-polyvinylidene fluoride emulsion. The average particle size of the resulting emulsion was 548 nm.
实施例2Example 2
水性含氟聚合物乳液的制备步骤：Preparation steps of aqueous fluoropolymer emulsion:
(1)在1000rpm的搅拌状态下，将0.2g数均分子量约为22，000的聚乙二醇缓慢加入到199.8g二甲基亚砜中，溶胀1小时后，升温至80℃，溶解1小时后，得到聚乙二醇溶液。(1) Under the stirring state of 1000 rpm, 0.2 g of polyethylene glycol with a number average molecular weight of about 22,000 was slowly added to 199.8 g of dimethyl sulfoxide, and after swelling for 1 hour, the temperature was raised to 80 ° C and dissolved 1 After hours, a polyethylene glycol solution was obtained.
(2)在1000rpm的搅拌状态下，将0.1g数均分子量为200，000的偏氟乙烯-六氟丙烯共聚物缓慢加入到99.9g二甲基亚砜中，溶胀1小时后，升温至80℃，溶解完全，得到聚偏氟乙烯-六氟丙烯溶液。(2) Under the stirring state of 1000rpm, 0.1g of vinylidene fluoride-hexafluoropropylene copolymer with a number average molecular weight of 200,000 was slowly added to 99.9g of dimethyl sulfoxide, and after swelling for 1 hour, the temperature was raised to 80 ℃, the dissolution is complete, and a polyvinylidene fluoride-hexafluoropropylene solution is obtained.
(3)在1000rpm的搅拌条件下，将聚偏氟乙烯-六氟丙烯溶液与聚乙二醇溶液混合均匀，形成油相，油相浓度为0.1％。(3) Under the stirring condition of 1000 rpm, the polyvinylidene fluoride-hexafluoropropylene solution and the polyethylene glycol solution are uniformly mixed to form an oil phase, and the oil phase concentration is 0.1%.
(4)在500rpm的机械搅拌条件下，以50g/min的速度将油相慢速滴加到300ml水中，再搅拌50min，超滤除去二甲基亚砜，继续超滤浓缩至固含量为50％时，停止超滤，形成聚乙二醇-聚偏氟乙烯-六氟丙烯乳液。所形成乳液的平均粒径为243nm。(4) under the mechanical stirring condition of 500rpm, the oil phase was slowly added dropwise to 300ml of water at a speed of 50g/min, stirred for 50min again, the dimethyl sulfoxide was removed by ultrafiltration, and the ultrafiltration concentration was continued until the solid content was 50 %, stop ultrafiltration to form polyethylene glycol-polyvinylidene fluoride-hexafluoropropylene emulsion. The average particle size of the resulting emulsion was 243 nm.
实施例3Example 3
水性含氟聚合物乳液的制备步骤：Preparation steps of aqueous fluoropolymer emulsion:
(1)在1000rpm的搅拌状态下，将3g数均分子量为100，000的聚甲基纤维素钠缓慢加入到7gN-甲基吡咯烷酮中，溶胀1小时后，升温至80℃，溶解1小时后，得到聚甲基纤维素钠溶液。(1) Under the stirring state of 1000rpm, slowly add 3g of sodium polymethyl cellulose with a number average molecular weight of 100,000 to 7g of N-methylpyrrolidone, swell for 1 hour, heat up to 80°C, dissolve for 1 hour , to obtain a sodium polymethylcellulose solution.
(2)在800rpm的搅拌状态下，将0.3g数均分子量为300，000的偏氟乙烯-四氟乙烯共聚物缓慢加入到0.7g二甲基亚砜中，溶胀1小时后，升温至80℃，溶解完全，得到聚偏氟乙烯-四氟乙烯溶液。(2) Under the stirring state of 800 rpm, slowly add 0.3 g of vinylidene fluoride-tetrafluoroethylene copolymer with a number average molecular weight of 300,000 to 0.7 g of dimethyl sulfoxide, and after swelling for 1 hour, the temperature is raised to 80 °C, the dissolution is complete, and a polyvinylidene fluoride-tetrafluoroethylene solution is obtained.
(3)在1000rpm的搅拌条件下，将聚偏氟乙烯-四氟乙烯溶液与聚甲基纤维素钠溶液混合均匀，形成油相，油相浓度为30％。(3) Under the stirring condition of 1000 rpm, the polyvinylidene fluoride-tetrafluoroethylene solution and the polymethyl cellulose sodium solution are mixed uniformly to form an oil phase, and the oil phase concentration is 30%.
(4)在500rpm的机械搅拌条件下，以0.1g/min的速度将油相慢速滴加到1100ml水相中，再搅拌40min，超滤除去N-甲基吡咯烷酮和二甲基亚砜，继续超滤浓缩至固含量为15％时，停止超滤，形成聚甲基纤维素钠-聚偏氟乙烯-四氟乙烯乳液，所形成乳液的平均粒径为347nm。(4) under the mechanical stirring condition of 500rpm, the oil phase was slowly added dropwise to the 1100ml water phase at a speed of 0.1g/min, and then stirred for 40min, and N-methylpyrrolidone and dimethyl sulfoxide were removed by ultrafiltration, When the ultrafiltration was continued and concentrated to a solid content of 15%, the ultrafiltration was stopped to form a polymethylcellulose sodium-polyvinylidene fluoride-tetrafluoroethylene emulsion, and the average particle size of the formed emulsion was 347 nm.
实施例4Example 4
水性含氟聚合物乳液的制备步骤：Preparation steps of aqueous fluoropolymer emulsion:
(1)在300rpm的搅拌状态下，将10g葡萄糖缓慢加入到90g纯水中，溶解10分钟后，得到葡萄糖溶液。(1) In a stirring state of 300 rpm, 10 g of glucose was slowly added to 90 g of pure water, and dissolved for 10 minutes to obtain a glucose solution.
(2)在800rpm的搅拌状态下，将1g数均分子量为500，000的偏氟乙烯-四氟乙烯共聚物缓慢加入到10g二甲基乙酰胺中，溶胀1小时后，升温至80℃，溶解完全，得到聚偏氟乙烯-四氟乙烯溶液。(2) Under the stirring state of 800rpm, 1g of vinylidene fluoride-tetrafluoroethylene copolymer with a number average molecular weight of 500,000 was slowly added to 10g of dimethylacetamide, and after swelling for 1 hour, the temperature was raised to 80°C, The dissolution was complete to obtain a polyvinylidene fluoride-tetrafluoroethylene solution.
(3)在1000rpm的搅拌条件下，将聚偏氟乙烯-四氟乙烯溶液与葡萄糖溶液混合均匀，形成油相，油相浓度为10％。(3) Under the stirring condition of 1000 rpm, the polyvinylidene fluoride-tetrafluoroethylene solution and the glucose solution are mixed uniformly to form an oil phase, and the concentration of the oil phase is 10%.
(4)在500rpm的机械搅拌条件下，以5g/min的速度将油相慢速滴加到300ml水中，再搅拌10min，超滤除去二甲基乙酰胺，继续超滤浓缩至固含量为18％时，停止超滤，形成葡萄糖-聚偏氟乙烯-四氟乙烯乳液，所得乳液平均粒径为689nm。(4) under the mechanical stirring condition of 500rpm, the oil phase was slowly added dropwise to 300ml of water at a speed of 5g/min, and then stirred for 10min, and the dimethylacetamide was removed by ultrafiltration, and continued ultrafiltration and concentrated to a solid content of 18 %, the ultrafiltration was stopped to form a glucose-polyvinylidene fluoride-tetrafluoroethylene emulsion, and the average particle size of the obtained emulsion was 689 nm.
实施例5Example 5
水性含氟聚合物乳液的制备步骤：Preparation steps of aqueous fluoropolymer emulsion:
(1)在300rpm的搅拌状态下，将4g数均分子量为200,000的水解淀粉缓慢加入到96gN-甲基吡咯烷酮中，溶胀30分钟后，加热至80℃，溶解2小时，得到水解淀粉溶液。(1) Under the stirring state of 300rpm, 4g of hydrolyzed starch with a number-average molecular weight of 200,000 was slowly added to 96g of N-methylpyrrolidone, and after swelling for 30 minutes, heated to 80° C. and dissolved for 2 hours to obtain a hydrolyzed starch solution.
(2)在800rpm的搅拌状态下，将2g数均分子量为200，000的偏氟乙烯-三氟氯乙烯共聚物缓慢加入到30gN-甲基吡咯烷酮中，溶胀1小时后，升温至80℃，溶解完全，得到聚偏氟乙烯-三氟氯乙烯溶液。(2) under the stirring state of 800rpm, 2g of vinylidene fluoride-chlorotrifluoroethylene copolymer with a number average molecular weight of 200,000 was slowly added to 30g of N-methylpyrrolidone, and after swelling for 1 hour, the temperature was raised to 80°C, The dissolution was complete to obtain a polyvinylidene fluoride-chlorotrifluoroethylene solution.
(3)在1000rpm的搅拌条件下，将聚偏氟乙烯-三氟氯乙烯溶液与水解淀粉溶液混合均匀，形成油相，油相浓度为4.58％。(3) Under the stirring condition of 1000 rpm, the polyvinylidene fluoride-chlorotrifluoroethylene solution and the hydrolyzed starch solution are uniformly mixed to form an oil phase, and the oil phase concentration is 4.58%.
(4)在1000rpm的机械搅拌条件下，以5g/min的速度将油相慢速滴加到500ml水中，再搅拌10min，超滤除去N-甲基吡咯烷酮，继续超滤浓缩至固含量为20％时，停止超滤，形成水解淀粉-聚偏氟乙烯-三氟氯乙烯乳液，所得乳液平均粒径为456nm(4) under the mechanical stirring condition of 1000rpm, the oil phase was slowly added dropwise to 500ml water at a speed of 5g/min, stirred for 10min again, the N-methylpyrrolidone was removed by ultrafiltration, and the ultrafiltration concentration was continued until the solid content was 20 %, the ultrafiltration was stopped to form a hydrolyzed starch-polyvinylidene fluoride-chlorotrifluoroethylene emulsion, and the average particle size of the obtained emulsion was 456 nm
实施例6Example 6
水性含氟聚合物乳液的制备步骤：Preparation steps of aqueous fluoropolymer emulsion:
(1)在300rpm的搅拌状态下，将10g数均分子量为600，000的水解淀粉缓慢加入到94gN-甲基吡咯烷酮中，溶胀30分钟后，加热至80℃，溶解2小时，得到水解淀粉溶液。(1) under the stirring state of 300rpm, the hydrolyzed starch that 10g number average molecular weight is 600,000 is slowly added in 94g N-methyl pyrrolidone, after swelling 30 minutes, be heated to 80 ℃, dissolve 2 hours, obtain hydrolyzed starch solution .
(2)在800rpm的搅拌状态下，将3g数均分子量为200，000的偏氟乙烯-三氟氯乙烯共聚物缓慢加入到30gN-甲基吡咯烷酮中，溶胀1小时后，升温至80℃，溶解完全，得到聚偏氟乙烯-三氟氯乙烯溶液。(2) under the stirring state of 800rpm, slowly add 3g of vinylidene fluoride-chlorotrifluoroethylene copolymer with number average molecular weight of 200,000 to 30g of N-methylpyrrolidone, and after swelling for 1 hour, heat up to 80°C, The dissolution was complete to obtain a polyvinylidene fluoride-chlorotrifluoroethylene solution.
(3)在1000rpm的搅拌条件下，将聚偏氟乙烯-三氟氯乙烯溶液与水解淀粉溶液混合均匀，再加入0.3g丙二醇苯醚(PPH)形成油相，油相浓度为9.77％。(3) Under the stirring condition of 1000rpm, the polyvinylidene fluoride-chlorotrifluoroethylene solution and the hydrolyzed starch solution were mixed uniformly, and then 0.3 g of propylene glycol phenyl ether (PPH) was added to form an oil phase, and the oil phase concentration was 9.77%.
(4)在1000rpm的机械搅拌条件下，以5g/min的速度将油相慢速滴加到500ml水中，再搅拌10min，超滤除去N-甲基吡咯烷酮，继续超滤浓缩至固含量为20％时，停止超滤，形成水解淀粉-聚偏氟乙烯-三氟氯乙烯乳液，所得乳液平均粒径为357nm。(4) under the mechanical stirring condition of 1000rpm, the oil phase was slowly added dropwise to 500ml water at a speed of 5g/min, stirred for 10min again, the N-methylpyrrolidone was removed by ultrafiltration, and the ultrafiltration concentration was continued until the solid content was 20 %, the ultrafiltration was stopped to form a hydrolyzed starch-polyvinylidene fluoride-chlorotrifluoroethylene emulsion, and the average particle size of the obtained emulsion was 357 nm.
对比例1：其它与实施例1相同，只是将实施例1中的2g数均分子量约为100，000聚乙烯醇改为1g，无法成功制备聚合物乳液。Comparative Example 1: Others were the same as in Example 1, except that the number average molecular weight of 2g in Example 1 was changed to 1g of polyvinyl alcohol of about 100,000, but the polymer emulsion could not be successfully prepared.
对比例2：其它与实施例2相同，只是将第四步中的转速由500rpm调至200rpm，无法成功制备聚合物乳液，制备的聚合物乳液有大量析出。Comparative Example 2: Others are the same as Example 2, except that the rotation speed in the fourth step is adjusted from 500 rpm to 200 rpm, the polymer emulsion cannot be successfully prepared, and the prepared polymer emulsion has a large amount of precipitation.
对比例3：其它与实施例3相同，只是第四步滴加速度以由0.1g/min调至100g/min能够制备聚合物乳液，但聚合物乳液有大量析出，稳定性低。Comparative Example 3: Others are the same as Example 3, except that the dropping rate in the fourth step can be adjusted from 0.1 g/min to 100 g/min to prepare a polymer emulsion, but the polymer emulsion has a large amount of precipitation and low stability.
在本说明书的描述中，参考术语“一个实施例”、“一些实施例”、“示例”、“具体示例”、或“一些示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例或示例中。在本说明书中，对上述术语的示意性表述不必须针对的是相同的实施例或示例。而且，描述的具体特征、结构、材料或者特点可以在任一个或多个实施例或示例中以合适的方式结合。此外，在不相互矛盾的情况下，本领域的技术人员可以将本说明书中描述的不同实施例或示例以及不同实施例或示例的特征进行结合和组合。In the description of this specification, description with reference to the terms "one embodiment," "some embodiments," "example," "specific example," or "some examples", etc., mean specific features described in connection with the embodiment or example , structure, material or feature is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, those skilled in the art may combine and combine the different embodiments or examples described in this specification, as well as the features of the different embodiments or examples, without conflicting each other.
尽管上面已经示出和描述了本发明的实施例，可以理解的是，上述实施例是示例性的，不能理解为对本发明的限制，本领域的普通技术人员在本发明的范围内可以对上述实施例进行变化、修改、替换和变型。Although the embodiments of the present invention have been shown and described above, it should be understood that the above-mentioned embodiments are exemplary and should not be construed as limiting the present invention. Embodiments are subject to variations, modifications, substitutions and variations.
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| CN1353130A (en) * | 2001-11-21 | 2002-06-12 | 中国科学院生态环境研究中心 | High-molecular microspheres or acicular microparticles with uniform granularity and its shaping process |
| US20060128872A1 (en) * | 2003-11-17 | 2006-06-15 | 3M Innovative Properties Company | Aqueous Dispersions of Polytetrafluoroethylene Having a Low Amount of Fluorinated Surfactant |
| CN101434674A (en) * | 2007-11-12 | 2009-05-20 | 上海博泰氟材料有限公司 | Fluorine-containing water-dilutable resin prepared by nucleocapsid emulsion multicomponent copolymerization and coating thereof |
| CN102458640A (en) * | 2009-06-05 | 2012-05-16 | 新加坡南洋理工大学 | Multi-phase microparticles and method of manufacturing multi-phase microparticles |
| CN105017750A (en) * | 2014-04-28 | 2015-11-04 | 乐凯胶片股份有限公司 | Water-based aromatic polyamide emulsion, preparation method and application of water-based aromatic polyamide emulsion |
| CN105273444A (en) * | 2014-07-23 | 2016-01-27 | 乐凯胶片股份有限公司 | Slurry composition and lithium ion battery diaphragm containing same |
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| CN111816879B (en) * | 2020-07-27 | 2021-11-16 | 日照广大建筑材料有限公司 | Lithium ion battery cathode binder, slurry and cathode material thereof |
| CN112851969A (en) * | 2021-01-08 | 2021-05-28 | 中国乐凯集团有限公司 | Polymer emulsion and method and apparatus for preparing the same |
| CN115117356A (en) * | 2022-08-30 | 2022-09-27 | 宁德时代新能源科技股份有限公司 | Core-shell structure polymer, preparation method and application thereof, positive electrode slurry, secondary battery, battery module, battery pack and electric device |
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