WO2024020782A1 - 一种非氟表面活性剂及其制备方法和应用 - Google Patents
一种非氟表面活性剂及其制备方法和应用 Download PDFInfo
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- WO2024020782A1 WO2024020782A1 PCT/CN2022/107935 CN2022107935W WO2024020782A1 WO 2024020782 A1 WO2024020782 A1 WO 2024020782A1 CN 2022107935 W CN2022107935 W CN 2022107935W WO 2024020782 A1 WO2024020782 A1 WO 2024020782A1
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- Prior art keywords
- fluorine
- fluorine surfactant
- preparation
- initiator
- surfactant
- Prior art date
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- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000004094 surface-active agent Substances 0.000 claims abstract description 55
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 50
- 239000011737 fluorine Substances 0.000 claims abstract description 50
- 229920000642 polymer Polymers 0.000 claims abstract description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 8
- 239000008346 aqueous phase Substances 0.000 claims abstract description 6
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000003999 initiator Substances 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 12
- 239000000839 emulsion Substances 0.000 claims description 10
- 229920002313 fluoropolymer Polymers 0.000 claims description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 7
- 239000004811 fluoropolymer Substances 0.000 claims description 7
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 5
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 claims description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229910001414 potassium ion Inorganic materials 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 229910001415 sodium ion Inorganic materials 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 3
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 24
- 239000012074 organic phase Substances 0.000 description 18
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- -1 polytetrafluoroethylene Polymers 0.000 description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000002390 rotary evaporation Methods 0.000 description 5
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical class [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 5
- XZPVPNZTYPUODG-UHFFFAOYSA-M sodium;chloride;dihydrate Chemical class O.O.[Na+].[Cl-] XZPVPNZTYPUODG-UHFFFAOYSA-M 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229920001774 Perfluoroether Polymers 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- YFSUTJLHUFNCNZ-UHFFFAOYSA-M 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctane-1-sulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-M 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 231100000693 bioaccumulation Toxicity 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000010702 perfluoropolyether Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000006552 photochemical reaction Methods 0.000 description 2
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 2
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 2
- 229940085675 polyethylene glycol 800 Drugs 0.000 description 2
- 229920002620 polyvinyl fluoride Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 1
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 1
- 229920002593 Polyethylene Glycol 800 Polymers 0.000 description 1
- 102100038239 Protein Churchill Human genes 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 150000001265 acyl fluorides Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000012648 alternating copolymerization Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical group 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- UZUFPBIDKMEQEQ-UHFFFAOYSA-N perfluorononanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F UZUFPBIDKMEQEQ-UHFFFAOYSA-N 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 description 1
- 229940057838 polyethylene glycol 4000 Drugs 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- YLQIJFPHMPTBGU-UHFFFAOYSA-M potassium;ethenesulfonate Chemical compound [K+].[O-]S(=O)(=O)C=C YLQIJFPHMPTBGU-UHFFFAOYSA-M 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- KTNWCLLNYPPCQT-UHFFFAOYSA-M sodium but-2-ene-2-sulfonate Chemical compound CC(=CC)S(=O)(=O)[O-].[Na+] KTNWCLLNYPPCQT-UHFFFAOYSA-M 0.000 description 1
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 description 1
- CPJUXKYRSFYJPS-UHFFFAOYSA-M sodium;prop-1-ene-2-sulfonate Chemical compound [Na+].CC(=C)S([O-])(=O)=O CPJUXKYRSFYJPS-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F14/00—Homopolymers and 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F18/00—Homopolymers and 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 acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
Definitions
- This application belongs to the field of chemical synthesis technology, and specifically relates to a non-fluorine surfactant and its preparation method and application.
- Fluoropolymers have excellent heat resistance, chemical resistance, durability and weather resistance, and have been widely used in chemical industry, petroleum, textile, food, papermaking, medicine, electronics, machinery and other fields.
- Such polymers mainly include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), polyvinyl fluoride (PVF), polyperfluoroethylene-propylene (FEP), and fusible polymers.
- PTFE polytetrafluoroethylene
- PVDF polyvinylidene fluoride
- PCTFE polychlorotrifluoroethylene
- PVF polyvinyl fluoride
- FEP polyperfluoroethylene-propylene
- fusible polymers mainly include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), polyvinyl fluoride (PVF), polyper
- PFOA perfluorooctyl carboxylate
- PFOS perfluorooctane sulfonate
- CN103073410A discloses a method for preparing a fluoroether carboxylic acid surfactant.
- Patent CN114031762A discloses a preparation process of perfluoropolyether surfactant and perfluoropolyether surfactant. Hexafluoropropylene, chlorotrifluoroethylene and oxygen are first used for photochemical reaction to obtain a crude product, which is then deperoxygenated and hydrolyzed. , and after neutralization, perfluoropolyether surfactant is obtained.
- fluoropolymers produced using the above-mentioned surfactants will still have fluorine compound residues and are still bioaccumulative to a certain extent, which does not meet the requirements for the development of green chemistry.
- international fluorochemical giants Solvay and DuPont have announced that they will accelerate the elimination of fluorosurfactants and completely solve the problem of bioaccumulation of fluorosurfactants. Therefore, it is urgent to carry out research on non-fluorinated surfactants.
- the purpose of the present invention is to provide a non-fluorine surfactant and its preparation method and application.
- the non-fluorinated surfactant has a good effect of reducing the surface tension of the aqueous phase system, and can replace the fluorinated surfactant and be used to prepare fluorinated polymers by aqueous emulsion polymerization.
- the present invention adopts the following technical solutions:
- the present invention provides a non-fluorine surfactant, which is a polymer whose main chain contains the following structural units:
- R 1 , R 2 , R 4 , R 5 , and R 6 are each independently a hydrogen atom or a C 1 to C 3 alkyl group
- R 3 is a hydrogen atom, NH 4 + or a monovalent metal ion
- n is an integer from 10 to 150 (for example, it can be 10, 15, 20, 30, 40, 50, 60, 80, 100, 120, 130 or 150, etc.).
- non-fluorine means that it does not contain fluorine.
- the structural formula of the non-fluorine surfactant provided by the present invention is as follows: Formula I:
- each of R 1 , R 2 , R 4 , R 5 , and R 6 is independently a hydrogen atom, a methyl group or an ethyl group.
- the molar ratio of structural unit A, structural unit B, structural unit C and structural unit D is (1.0 ⁇ 1.6):(1.2 ⁇ 1.5):1:(0.2 ⁇ 0.6).
- the molecular weight of the non-fluorine surfactant is 200,000 to 800,000; for example, it can be 200,000, 250,000, 300,000, 350,000, 400,000, 450,000, 500,000, 550,000, 600,000, 650,000, 700,000, 750,000 or 800,000 etc.
- the monovalent metal ion is sodium ion or potassium ion.
- the present invention provides a method for preparing the non-fluorine surfactant as described in the first aspect, the preparation method comprising the following steps:
- polyethylene glycol (PEG) It connects the structural units D through an esterification reaction with carboxyl groups.
- the polyethylene glycol used in the present invention can be PEG-400, PEG-800, PEG-1000, PEG-2000 or PEG-4000, etc.
- the initiator is selected from one or more of ammonium persulfate, sodium persulfate, potassium persulfate, di-tert-butyl peroxide and dibenzoyl peroxide.
- the initiator is used in an amount of the compound 0.1 to 0.5% of the total mass; for example, it can be 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45% or 0.5%, etc.
- the compound and polyethylene glycol are added by one-time addition, and the compound The initiator and the initiator are added dropwise in the form of an aqueous solution.
- the dropping time is 0.5-1.5h; for example, it can be 0.5h, 0.6h, 0.8h, 1h, 1.2h, 1.3h or 1.5h, etc.
- the reaction temperature is 60-120°C; for example, it can be 60°C, 70°C, 80°C, 90°C, 100°C, 110°C or 120°C, etc.
- the reaction time is 4-10h; for example, it can be 4h, 5h, 6h, 7h, 8h, 9h or 10h, etc.
- the reaction time is 4-10 h excluding the time of dripping.
- the preparation method of the non-fluorine surfactant may also include a purification operation to obtain a pure non-fluorine surfactant product.
- the present invention has no special limitations on the purification method.
- purification can be carried out according to the following steps: after the reaction is completed, separate the lower organic phase solution, add chloroform to obtain a mixed solution; wash the mixed solution with saturated sodium sulfite aqueous solution, saturated brine and deionized water respectively, and separate to obtain the second solution.
- the organic phase solution is then dried with anhydrous sodium sulfate; finally, the non-fluorine surfactant is obtained after filtration and rotary evaporation.
- the present invention provides an application of the non-fluorine surfactant as described in the first aspect in the preparation of fluorine-containing polymers by aqueous emulsion polymerization.
- the present invention provides a method for preparing fluorine-containing polymers.
- the preparation method includes: subjecting fluorine-containing monomers to an aqueous emulsion polymerization in an aqueous phase containing the non-fluorinated surfactant described in the first aspect, The fluoropolymer is produced.
- the fluorine-containing monomer is selected from one or more of tetrafluoroethylene, hexafluoropropylene, vinyl fluoride, vinylidene fluoride, trifluoroethylene and chlorotrifluoroethylene.
- the amount of the non-fluorinated surfactant is 0.008-0.2% of the mass of the fluoropolymer; for example, it can be 0.008%, 0.01%, 0.02%, 0.03%, 0.05%, 0.06 %, 0.08%, 0.1%, 0.12%, 0.13%, 0.15%, 0.16%, 0.18% or 0.2%, etc.
- the present invention has the following beneficial effects:
- the non-fluorine surfactant provided by the invention has a good effect of reducing the surface tension of the aqueous phase system, and can significantly reduce the surface tension of the aqueous phase at a lower concentration.
- the non-fluorinated surfactant is more environmentally friendly than the fluorinated surfactant and can replace the fluorinated surfactant for preparing fluorinated polymers by aqueous emulsion polymerization.
- the prepared fluorinated polymer emulsion is stable and has no demulsification phenomenon.
- This embodiment provides a non-fluorine surfactant, and its preparation method is as follows:
- This embodiment provides a non-fluorine surfactant, and its preparation method is as follows:
- This embodiment provides a non-fluorine surfactant, and its preparation method is as follows:
- This embodiment provides a non-fluorine surfactant, and its preparation method is as follows:
- Application Examples 1-4 respectively use the non-fluorine surfactant provided in Examples 1-4 to prepare polyperfluoroethylene-propylene. The steps are as follows:
- the volume ratio of propylene is 32:68) until the pressure in the reactor reaches 3.5MPa, add 20g of ammonium persulfate dissolved in 100mL of water, and add a mixed monomer of tetrafluoroethylene and hexafluoropropylene (tetrafluoropropylene) during the reaction.
- the volume ratio of ethylene to hexafluoropropylene is 96:4) and the pressure in the reaction kettle is controlled to 3.8MPa.
- the solid content of the emulsion reaches 30%, the reaction ends and a polyperfluoroethylene-propylene emulsion is obtained. No coagulation or precipitation of the emulsion is observed. sign.
- Emulsion stability test Test according to GB/T1603-2001 test standard. The test results are shown in Table 1:
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
Abstract
本发明提供了一种非氟表面活性剂及其制备方法和应用。所述非氟表面活性剂为聚合物，其主链中包含如下结构单元：结构单元A、结构单元B、结构单元C、结构单元D；其中，所述结构单元D相互之间通过(I)连接；R1、R2、R4、R5、R6各自独立地为氢原子或C1～C3烷基；R3为氢原子、NH4 +或一价金属离子；n为10-150的整数。本发明提供的非氟表面活性剂具有良好的降低水相体系表面张力的作用，可代替含氟表面活性剂，用于制备含氟聚合物。
Description
本申请属于化工合成技术领域，具体涉及一种非氟表面活性剂及其制备方法和应用。
含氟聚合物具有优良的耐热性、耐化学腐蚀性、耐久性和耐候性等性能，在化工、石油、纺织、食品、造纸、医学、电子、机械等领域得到了广泛应用。此类聚合物主要有聚四氟乙烯(PTFE)、聚偏氟乙烯(PVDF)、聚三氟氯乙烯(PCTFE)、聚氟乙烯(PVF)、聚全氟乙丙烯(FEP)、可熔性聚四氟乙烯(PFA)等。
目前，工业生产含氟聚合物，主要是以全氟辛基羧酸盐(PFOA)、全氟辛基磺酸盐(PFOS)或其衍生物作为表面活性剂，通过水性乳液聚合法进行制备。这两种表面活性剂是目前世界上发现最难降解的有机污染物，它们在周围环境中历久不散，并具有很高的生物累积性，逐渐遭到世界各国环保组织的禁用。许多国家在研发替代PFOS和PFOA的新型氟碳表面活性剂方面做了大量的工作，取得了巨大的进展。例如CN103073410A公开了一种氟醚羧酸表面活性剂的制备方法，通过含氟烯烃单体和氧气经过紫外光引发光化反应生成氟醚酰氯和氟醚酰氟，再水解生成氟醚羧酸。专利CN114031762A公开了一种全氟聚醚表面活性剂的制备工艺及全氟聚醚表面活性剂，先利用六氟丙烯、三氟氯乙烯和氧气进行光化学反应得到粗产物，然后脱过氧、水解、中和后得到全氟聚醚表面活性剂。
但是利用上述表面活性剂生产的氟聚合物仍会有氟化合物残留，仍然具有一定的生物累积性，不符合绿色化学发展的要求。近日，国际氟化工巨头索尔维和杜邦公司纷纷宣布加速淘汰含氟表面活性剂，彻底解决含氟表面活性剂的生物累计问题。因此，开展非氟表面活性 剂的研究迫在眉睫。
发明内容
针对相关技术存在的不足，本发明的目的在于提供一种非氟表面活性剂及其制备方法和应用。该非氟表面活性剂具有良好的降低水相体系表面张力的作用，可代替含氟表面活性剂，用于水性乳液聚合法制备含氟聚合物。
为达此目的，本发明采用以下技术方案：
第一方面，本发明提供一种非氟表面活性剂，所述非氟表面活性剂为聚合物，其主链中包含如下结构单元：
其中，所述结构单元D相互之间通过
连接；
R
1、R
2、R
4、R
5、R
6各自独立地为氢原子或C
1～C
3烷基；
R
3为氢原子、NH
4
+或一价金属离子；
n为10-150的整数(例如可以是10、15、20、30、40、50、60、80、100、120、130或150等)。
本发明中，
代表基团的连接键。
本发明中，所述“非氟”是指不含氟。本发明提供的非氟表面活性剂的结构式如下式I所示：
需要说明的是，由于多种单体聚合形成的共聚物存在交替共聚、无规共聚、嵌段共聚等不同的键合方式，以及不同的立体构型，无法通过结构式进行表示，因此式I仅用于说明非氟表面活性剂的分子链由哪些结构单元构成，不代表非氟表面活性剂的真实结构。
在本发明一些实施方式中，所述R
1、R
2、R
4、R
5、R
6各自独立地为氢原子、甲基或乙基。
在本发明一些实施方式中，所述结构单元A、结构单元B、结构单元C和结构单元D的摩尔比为(1.0～1.6):(1.2～1.5):1:(0.2～0.6)。
在本发明一些实施方式中，所述非氟表面活性剂的分子量为20～80万；例如可以是20万、25万、30万、35万、40万、45万、50万、55万、60万、65万、70万、75万或80万等。
在本发明一些实施方式中，所述一价金属离子为钠离子或钾离子。
第二方面，本发明提供一种如第一方面所述的非氟表面活性剂的制备方法，所述制备方法包括如下步骤：
以化合物
和聚乙二醇为原料，在引发剂的作用下，在水中进行反应，生成所述非氟表面活性剂。
其中，聚乙二醇(PEG)的结构式为
其通过与羧基的酯化反应将结构单元D连接起来。本发明中采用的聚乙二醇可以是PEG-400、PEG-800、PEG-1000、PEG-2000或PEG-4000等。
在本发明一些实施方式中，所述引发剂选自过硫酸铵、过硫酸钠、过硫酸钾、过氧化二叔丁基和过氧化二苯甲酰中的一种或多种。
在本发明一些实施方式中，所述引发剂的用量为所述化合物
总质量的0.1～0.5％；例如可以是0.1％、0.15％、0.2％、0.25％、0.3％、0.35％、0.4％、0.45％或0.5％等。
在本发明一些实施方式中，所述化合物
和聚乙二醇是通过一次性添加的方式进行投料，所述化合物
和引发剂是以水溶液的形式通过滴加的方式进行投料。
在本发明一些实施方式中，所述滴加的时间为0.5-1.5h；例如可以是0.5h、0.6h、0.8h、1h、1.2h、1.3h或1.5h等。
在本发明一些实施方式中，所述反应的温度为60-120℃；例如可以是60℃、70℃、80℃、90℃、100℃、110℃或120℃等。
在本发明一些实施方式中，所述反应的时间为4-10h；例如可以是4h、5h、6h、7h、8h、9h或10h等。
需要说明的是，本发明中当通过滴加的方式进行投料时，所述反应时间为4-10h不包括滴加的时间。
在本发明一些实施方式中，所述非氟表面活性剂的制备方法还可以包括提纯操作，以获得纯净的非氟表面活性剂产品。
本发明对于提纯的方法没有特殊限制。示例性地，可以按照如下 步骤进行提纯：反应结束后，分出下层有机相溶液，加入氯仿得到混合溶液；将混合溶液分别用饱和亚硫酸钠水溶液、饱和盐水和去离子水进行洗涤，分离得到第二有机相溶液；然后采用无水硫酸钠对第二有机相溶液进行干燥；最后经过过滤、旋转蒸发后得到非氟表面活性剂。
第三方面，本发明提供一种如第一方面所述的非氟表面活性剂在水性乳液聚合法制备含氟聚合物中的应用。
第四方面，本发明提供一种含氟聚合物的制备方法，所述制备方法包括：使含氟单体在含有第一方面所述的非氟表面活性剂的水相中进行水性乳液聚合，生成所述含氟聚合物。
在本发明一些实施方式中，所述含氟单体选自四氟乙烯、六氟丙烯、氟乙烯、偏氟乙烯、三氟乙烯和三氟氯乙烯中的一种或多种。
在本发明一些实施方式中，所述非氟表面活性剂的用量为所述含氟聚合物质量的0.008～0.2％；例如可以是0.008％、0.01％、0.02％、0.03％、0.05％、0.06％、0.08％、0.1％、0.12％、0.13％、0.15％、0.16％、0.18％或0.2％等。
与相关技术相比，本发明具有以下有益效果：
本发明提供的非氟表面活性剂具有良好的降低水相体系表面张力的作用，在较低的浓度下即可大幅降低水相的表面张力。该非氟表面活性剂比含氟表面活性剂更加环保，可代替含氟表面活性剂，用于水性乳液聚合法制备含氟聚合物，且制备的含氟聚合物乳液稳定，无破乳现象。
下面通过具体实施方式来进一步说明本发明的技术方案。本领域技术人员应该明了，所述具体实施方式仅仅是帮助理解本发明，不应视为对本发明的具体限制。
实施例1
本实施例提供一种非氟表面活性剂，其制备方法如下：
向5L高压反应釜中加入500mL去离子水和1600g聚乙二醇800，氮气置换三次后向反应釜中冲入896g CH
3CH
2CH＝CH
2。80℃下使用计量泵同时缓慢向反应釜中加入单体溶液(溶解在500mL去离子水中的360g乙烯基磺酸钠和860g CH
3CH＝CHCOOH)和引发剂溶液(溶解在100mL去离子水中的8g过硫酸铵)，控制在1h内加完。加料完毕后，在120℃下反应4h。反应结束后，排出未反应的气体，使用分液漏斗分出下层有机相溶液，在有机相中加入500mL氯仿得到混合溶液；将混合溶液分别用饱和亚硫酸钠水溶液、饱和盐水和去离子水进行洗涤，分离得到有机相溶液；然后采用无水硫酸钠对有机相溶液进行干燥；最后经过过滤、旋转蒸发后得到非氟表面活性剂D1，测得其数均分子量为320000，HLB值为17.5。
实施例2
本实施例提供一种非氟表面活性剂，其制备方法如下：
向5L高压反应釜中加入500mL去离子水和3200g聚乙二醇800，氮气置换三次后向反应釜中冲入336g乙烯。80℃下使用计量泵同时缓慢向反应釜中加入单体溶液(溶解在500mL去离子水中的2175g 1-甲基乙烯基磺酸钠和710g丙烯酸)和引发剂溶液(溶解在100mL去离子水中的16g过硫酸钠)，控制在1h内加完。加料完毕后，在100℃下反应6h。反应结束后，排出未反应的气体，使用分液漏斗分出下层有机相溶液，在有机相中加入500mL氯仿得到混合溶液；将混合溶液分别用饱和亚硫酸钠水溶液、饱和盐水和去离子水进行洗涤，分离得到有机相溶液；然后采用无水硫酸钠对有机相溶液进行干燥；最后经过过滤、旋转蒸发后得到非氟表面活性剂D2，测得其数均分子量为210000，HLB值为16.4。
实施例3
本实施例提供一种非氟表面活性剂，其制备方法如下：
向5L高压反应釜中加入500mL去离子水和2000g聚乙二醇 2000，氮气置换三次后向反应釜中冲入710g CH
3CH＝CHCH
2CH
3。80℃下使用计量泵同时缓慢向反应釜中加入单体溶液(溶解在500mL去离子水中的1896g 1-甲基丙烯基磺酸钠和710g丙烯酸)和引发剂溶液(溶解在100mL去离子水中的4g过硫酸钾)，控制在1h内加完。加料完毕后，在110℃下反应5h。反应结束后，排出未反应的气体，使用分液漏斗分出下层有机相溶液，在有机相中加入500mL氯仿得到混合溶液；将混合溶液分别用饱和亚硫酸钠水溶液、饱和盐水和去离子水进行洗涤，分离得到有机相溶液；然后采用无水硫酸钠对有机相溶液进行干燥；最后经过过滤、旋转蒸发后得到非氟表面活性剂D3，测得其数均分子量为550000，HLB值为15.9。
实施例4
本实施例提供一种非氟表面活性剂，其制备方法如下：
向5L高压反应釜中加入500mL去离子水和8000g聚乙二醇4000，氮气置换三次后向反应釜中冲入784g CH
3CH
2CH＝CH
2。80℃下使用计量泵同时缓慢向反应釜中加入单体溶液(溶解在500mL去离子水中的1898g乙烯基磺酸钾和1000g CH
3CH
2CH＝CH-COOH)和7g过氧化二叔丁基引发剂，控制在1h内加完。加料完毕后，在120℃下反应4h。反应结束后，排出未反应的气体，使用分液漏斗分出下层有机相溶液，在有机相中加入500mL氯仿得到混合溶液；将混合溶液分别用饱和亚硫酸钠水溶液、饱和盐水和去离子水进行洗涤，分离得到有机相溶液；然后采用无水硫酸钠对有机相溶液进行干燥；最后经过过滤、旋转蒸发后得到非氟表面活性剂D4，测得其数均分子量为460000，HLB值为18.3。
应用例1-4
应用例1-4分别使用实施例1-4提供的非氟表面活性剂制备聚全氟乙丙烯，步骤如下：
向50L反应釜中加入30kg去离子水，将反应釜抽真空，并用N
2置换至其氧含量≤30ppm。向反应釜中分别加入实施例1-4提供的非 氟表面活性剂1.8g，将反应釜加热至80℃，通入四氟乙烯和六氟丙烯的初始混合单体(四氟乙烯与六氟丙烯的体积比为32:68)至反应釜内的压力达到3.5MPa，加入溶解在100mL水中的20g过硫酸铵，反应过程中通过补加四氟乙烯和六氟丙烯的混合单体(四氟乙烯与六氟丙烯的体积比为96:4)控制反应釜内的压力为3.8MPa，当乳液固含量达到30％时结束反应，得到聚全氟乙丙烯乳液，没有观察到乳液凝结或沉淀的迹象。
乳液稳定性测试：根据GB/T1603-2001测试标准进行测试，测试结果如表1所示：
表1乳液稳定性测试结果
| 序号 | 表面活性剂 | 乳液稳定时间/s |
| 应用例1 | D1 | 420±8 |
| 应用例2 | D2 | 450±6 |
| 应用例3 | D3 | 460±10 |
| 应用例4 | D4 | 430±8 |
从应用例1-4制得的乳液状态和表1的测试结果可以看出，本发明提供的非氟表面活性剂可用于含氟聚合物的水性乳液聚合，且形成的乳液稳定性良好。
虽然，上文中已经用一般性说明、具体实施方式及试验，对本发明作了详尽的描述，但在本发明基础上，可以对之作一些修改或改进，这对本领域技术人员而言是显而易见的。因此，在不偏离本发明精神的基础上所做的这些修改或改进，均属于本发明要求保护的范围。
Claims (10)
- 一种非氟表面活性剂，其特征在于，所述非氟表面活性剂为聚合物，其主链中包含如下结构单元：
其中，所述结构单元D相互之间通过连接；
R 1、R 2、R 4、R 5、R 6各自独立地为氢原子或C 1～C 3烷基；R 3为氢原子、NH 4 +或一价金属离子；n为10-150的整数。 - 根据权利要求1所述的非氟表面活性剂，其中，所述R 1、R 2、R 4、R 5、R 6各自独立地为氢原子、甲基或乙基。
- 根据权利要求1或2所述的非氟表面活性剂，其中，所述结构单元A、结构单元B、结构单元C和结构单元D的摩尔比为(1.0～1.6):(1.2～1.5):1:(0.2～0.6)。
- 根据权利要求1-3任一项所述的非氟表面活性剂，其中，所述非氟表面活性剂的数均分子量为20～80万。
- 根据权利要求1-4任一项所述的非氟表面活性剂，其中，所述一价金属离子为钠离子或钾离子。
- 一种如权利要求1-5任一项所述的非氟表面活性剂的制备方法，其特征在于，所述制备方法包括如下步骤：以化合物和聚乙二醇为原料，在引发剂的作用下，在水中进行反应，生成所述非氟表面活性剂。
- 根据权利要求6所述的制备方法，其中，所述引发剂选自过硫酸铵、过硫酸钠、过硫酸钾、过氧化二叔丁基和过氧化二苯甲酰中 的一种或多种；优选地，所述引发剂的用量为所述化合物
总质量的0.1～0.5％；
优选地，所述化合物和聚乙二醇是通过一次性添加的方式进行投料，所述化合物
和引发剂是以水溶液的形式通过滴加的方式进行投料；
优选地，所述滴加的时间为0.5-1.5h。 - 根据权利要求6所述的制备方法，其中，所述反应的温度为60-120℃；优选地，所述反应的时间为4-10h。
- 一种如权利要求1-5任一项所述的非氟表面活性剂在水性乳液聚合法制备含氟聚合物中的应用。
- 一种含氟聚合物的制备方法，其特征在于，所述制备方法包括：使含氟单体在含有权利要求1-5任一项所述的非氟表面活性剂的水相中进行水性乳液聚合，生成所述含氟聚合物；优选地，所述含氟单体选自四氟乙烯、六氟丙烯、氟乙烯、偏氟乙烯、三氟乙烯和三氟氯乙烯中的一种或多种；优选地，所述非氟表面活性剂的用量为所述含氟聚合物质量的0.008～0.02％。
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| JP2015199944A (ja) * | 2014-03-31 | 2015-11-12 | ダイキン工業株式会社 | 含フッ素シード重合体粒子の水性分散液の製造方法 |
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| WO2021131996A1 (ja) * | 2019-12-25 | 2021-07-01 | ダイキン工業株式会社 | フルオロポリマーの製造方法 |
| CN114127131A (zh) * | 2019-07-23 | 2022-03-01 | 大金工业株式会社 | 含氟聚合物的制造方法、聚四氟乙烯组合物和聚四氟乙烯粉末 |
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| CN101787091A (zh) * | 2010-01-18 | 2010-07-28 | 上海三爱富新材料股份有限公司 | 一种含氟聚合物水性分散乳液及其制备方法 |
| JP2015199944A (ja) * | 2014-03-31 | 2015-11-12 | ダイキン工業株式会社 | 含フッ素シード重合体粒子の水性分散液の製造方法 |
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