CN115260375A - Environment-friendly fluorine-containing copolymer and preparation method thereof - Google Patents
Environment-friendly fluorine-containing copolymer and preparation method thereof Download PDFInfo
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- CN115260375A CN115260375A CN202211003411.7A CN202211003411A CN115260375A CN 115260375 A CN115260375 A CN 115260375A CN 202211003411 A CN202211003411 A CN 202211003411A CN 115260375 A CN115260375 A CN 115260375A
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- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 75
- 239000011737 fluorine Substances 0.000 title claims abstract description 73
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229920001577 copolymer Polymers 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 88
- 239000000178 monomer Substances 0.000 claims abstract description 69
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 42
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 41
- 239000003999 initiator Substances 0.000 claims abstract description 29
- 239000002904 solvent Substances 0.000 claims abstract description 23
- 239000003960 organic solvent Substances 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- 125000003158 alcohol group Chemical group 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 3
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 3
- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 125000002081 peroxide group Chemical group 0.000 claims 1
- 238000009826 distribution Methods 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 230000007774 longterm Effects 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000001704 evaporation Methods 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 description 17
- 238000000576 coating method Methods 0.000 description 17
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 7
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 7
- -1 aliphatic mercaptans Chemical class 0.000 description 6
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000379 polymerizing effect Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 150000002978 peroxides Chemical group 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 2
- SKYXLDSRLNRAPS-UHFFFAOYSA-N 1,2,4-trifluoro-5-methoxybenzene Chemical compound COC1=CC(F)=C(F)C=C1F SKYXLDSRLNRAPS-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- VUIWJRYTWUGOOF-UHFFFAOYSA-N 2-ethenoxyethanol Chemical compound OCCOC=C VUIWJRYTWUGOOF-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000012674 dispersion polymerization Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- KDBPJFGPBDDBGC-UHFFFAOYSA-N ethenoxymethanol Chemical compound OCOC=C KDBPJFGPBDDBGC-UHFFFAOYSA-N 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- NUKZAGXMHTUAFE-UHFFFAOYSA-N hexanoic acid methyl ester Natural products CCCCCC(=O)OC NUKZAGXMHTUAFE-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009439 industrial construction Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- WNZQDUSMALZDQF-UHFFFAOYSA-N isobenzofuranone Natural products C1=CC=C2C(=O)OCC2=C1 WNZQDUSMALZDQF-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 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
- C08F214/00—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
- C08F214/18—Monomers containing fluorine
- C08F214/24—Trifluorochloroethene
- C08F214/245—Trifluorochloroethene with non-fluorinated comonomers
- C08F214/247—Trifluorochloroethene with non-fluorinated comonomers with non-fluorinated vinyl ethers
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
- C08F2/06—Organic solvent
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- 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
- C08F214/00—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
- C08F214/18—Monomers containing fluorine
- C08F214/26—Tetrafluoroethene
- C08F214/265—Tetrafluoroethene with non-fluorinated comonomers
- C08F214/267—Tetrafluoroethene with non-fluorinated comonomers with non-fluorinated vinyl ethers
-
- 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
- C08F216/00—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
- C08F216/02—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 by an alcohol radical
- C08F216/04—Acyclic compounds
- C08F216/08—Allyl alcohol
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses an environment-friendly fluorine-containing copolymer which comprises the following components in parts by weight:
Description
Technical Field
The invention belongs to the field of chemical materials, particularly relates to a fluorine-containing copolymer and a preparation method thereof, and particularly relates to a preparation method of an environment-friendly fluorine-containing copolymer by solution free radical polymerization with chlorotrifluoroethylene or tetrafluoroethylene as a main component.
Background
Fluorine atoms have low polarizability, strong electronegativity, small van der waals radius and strong C — F bond energy, and thus exhibit excellent weather resistance, chemical resistance, water and oil repellency, durability, stain resistance and the like in the fluorocopolymer. The method is widely applied to the fields of industrial construction, aerospace, marine corrosion prevention and the like.
A fluorine-containing copolymer and a method for producing the same are disclosed, for example, a method for producing a fluorine-containing copolymer by copolymerizing chlorotrifluoroethylene or tetrafluoroethylene with a vinyl functional monomer in a solution by solution polymerization or dispersion polymerization (CN 113795519A), and a method for producing the same, in which a single-shot charge is used, the presence of a gas-phase monomer increases the initial pressure of the reaction, and the concentration of the comonomer is large, which is disadvantageous in controlling the reaction, and causes a problem that the molecular weight distribution is not uniform, and when a coating film is formed, the weather resistance and the solvent resistance are poor. Meanwhile, the prepared coating has heavy smell, and is not beneficial to body health and environment protection. For example, in emulsion polymerization (CN 1469912A, CN 1096477C, japanese patent application laid-open No. 50-4396), 1-difluoroethylene is copolymerized with a vinyl unsaturated monomer and then copolymerized with a functional monomer (e.g., a hydroxyl or acrylic monomer) to obtain a fluorine-containing copolymer. The presence of a non-fluorine-containing carboxylic acid monomer such as acrylic acid significantly hinders the polymerization reaction, and a large amount of various surfactants are used to reduce the size of polymer particles, and the use of acrylic monomer seed particles having a particle size of 50nm or less causes coagulation under high shear force, and the surfactant precipitates when an aqueous coating material is prepared, resulting in a problem that the water resistance and storage stability of the coating film are poor.
Therefore, it is desired to develop a method for producing an environmentally friendly fluorine-containing copolymer, which employs continuous addition of a gas-phase fluorine monomer, and has a low polymerization initiation pressure, is easy to control, and has a uniform molecular weight distribution, and the fluorine-containing copolymer uses an environmentally friendly solvent, can be cured at normal temperature, and has excellent solvent resistance, water resistance, long-term weatherability, gloss, and the like. So as to solve the technical defects of the prior fluorine-containing polymer manufacturing method.
Disclosure of Invention
In view of the drawbacks of the prior art, an object of the present invention is to provide an environmentally friendly fluorinated copolymer and a method for producing the same, and particularly to a method for producing a fluorinated copolymer by solution radical polymerization using chlorotrifluoroethylene or tetrafluoroethylene as a main component. The invention combines the characteristic that the fluorine monomer is in a gas phase, provides a method for continuously feeding the fluorine monomer, and has the advantages of simple and easily controlled process, uniform and adjustable molecular weight distribution, environment-friendly solvent used by the fluorine-containing copolymer prepared by the method, capability of being cured at normal temperature, excellent solvent resistance, water resistance, long-term weather resistance, gloss and the like.
In order to solve the technical problems, the invention adopts the following technical scheme:
the environment-friendly fluorine-containing copolymer comprises the following components in parts by weight:
further, the chain transfer agent is one or more of aliphatic mercaptan, dodecyl mercaptan and isopropanol.
The chain transfer agent is used for adjusting the relative molecular mass of the fluorine-containing copolymer and controlling the chain length of the fluorine-containing copolymer, has no influence on the reaction speed, and only shortens the chain length. Specific examples of the chain transfer agent include aliphatic mercaptans, dodecylmercaptans, and isopropyl alcohols, preferably isopropyl alcohol. The amount is 0.5-4%, preferably 0.5-1% of the total weight. The use amount is more than 0.5 percent, the molecular weight, the polymerization degree and the viscosity of the fluorine-containing copolymer can be effectively reduced, the use amount is more than 4 percent, the more branched chains of the polymer, the smaller the viscosity and the more residual quantity in the final product can be obtained.
Further, the initiator is a peroxide initiator.
The peroxide initiator of the present invention is not particularly limited as long as it is a compound containing a peroxy group (-O-), upon heating, the-O-bond breaks, splitting into two corresponding free radicals, thereby initiating polymerization of the monomer. Specific examples of the peroxide initiator include benzoyl peroxide, benzoyl tert-butyl peroxide, methyl ethyl ketone peroxide, phthalide peroxide, tert-butyl peroxide and the like. Benzoyl tert-butyl peroxide is preferred. The amount is 0.5-2%, preferably 1-1.5% of the total weight. The use amount is less than 0.5%, the vinyl-based monomer cannot be completely and effectively initiated, the use amount is more than 2%, the hardness of the coating film is reduced, the residual amount in the polymer is increased, and the storage stability of the polymer and the appearance of the coating film are influenced.
Further, the vinyl group-containing monomer is a monomer in which at least 1 hydrogen atom bonded to a carbon atom is substituted with a fluorine atom.
The fluororesin may be endowed with various properties such as weather resistance, solvent resistance, heat resistance, stain resistance and the like. Specific examples of the vinyl fluoromonomer (C) include Vinyl Fluoride (VF), tetrafluoroethylene (TFE), vinylidene fluoride (VdF), and Chlorotrifluoroethylene (CTFE), and preferably one of Tetrafluoroethylene (TFE) and Chlorotrifluoroethylene (CTFE). The amount is 20-45%, preferably 25-35% of the total weight. The dosage is more than 20 percent, the weather resistance of the coating film is excellent, and the dosage is more than 45 percent, which affects the dosage of other non-fluorine vinyl monomers and the processing and application performance of the coating.
Further, the vinyl non-fluorine monomer includes one or more of a vinyl non-fluorine monomer containing a hydroxyl group or an alcohol group but not containing a carboxyl group, a vinyl non-fluorine monomer containing a carboxyl group but not containing a hydroxyl group or an alcohol group, a vinyl non-fluorine monomer containing neither a carboxyl group nor a hydroxyl group or an alcohol group.
Specific examples of the vinyl non-fluorine monomer include hydroxyalkyl vinyl ethers (such as 2-hydroxyethyl vinyl ether, hydroxymethyl vinyl ether, and 4-hydroxybutyl vinyl ether), hydroxyalkyl vinyl esters, vinyl glycol ethers, allyl alcohol, and allyl group-containing derivatives; specific examples of the vinyl non-fluorine monomer include acrylic acid and butenoic acid, and specific examples of the vinyl non-fluorine monomer are not particularly limited as long as the monomer contains a vinyl non-fluorine and does not contain a carboxyl group, a hydroxyl group or an alcohol group. Examples of the vinyl non-fluorine monomer include cyclohexyl vinyl ether. The vinyl non-fluorine monomer is preferably allyl alcohol or an allyl group-containing derivative, and particularly preferably allyl alcohol, from the viewpoint of excellent copolymerizability and excellent weather resistance of the formed coating film; the vinyl non-fluorine monomer is preferably crotonic acid, and particularly preferably trans-crotonic acid. The vinyl non-fluorine monomer is preferably cyclohexyl vinyl ether monomer, and 3 or more kinds of vinyl non-fluorine monomers can be used. The vinyl non-fluorinated monomers are used in amounts of 3% to 15%, preferably 6% to 10% by weight, based on the total weight. The dosage is more than 3 percent, and the coating has good crosslinking with a curing agent, weather resistance, solvent resistance and the like. The vinyl non-fluorinated monomers are used in an amount of 0.5% to 5%, preferably 1% to 2%, of the total weight of the monomers. The dosage is less than 0.5 percent, the pigment and the filler in the coating can not play a good role in wetting and dispersing, the grinding time is long, the effect is poor, and the like. The vinyl non-fluorinated monomers are used in amounts of from 5% to 20%, preferably from 10% to 15%, by weight of the total monomers. The dosage is more than 5 percent, a coating film with high hardness can be achieved, the dosage of the monomer cannot exceed the upper limit value, otherwise, the dosage of other non-fluorine vinyl monomers is influenced, and the processing and application performance of the coating is influenced.
Further, the organic solvent comprises one or more of butyl acetate, toluene, xylene and methyl isobutyl ketone, and butyl acetate is preferred. The dosage is 30-70% of the total weight, preferably 40-50%, the dosage is less than 30%, the polymerization heat release is large, the temperature control operation is not easy, the later performance of the product is influenced, and the dosage is less than 70%, so that the resin with satisfactory performance can be obtained.
Further, the general structural formula of the environment-friendly solvent is CH 3 O-CO-[(CH 2 ) n -CO-] m -O-CH 3 M is less than or equal to 1, n is less than or equal to 4. Preferably N 1 (m =0, N = 0) or N 2 (m＝1，n＝2，3，4)，N 1 :N 2 1 to 1, preferably N 1 :N 2 1 to 6, N is particularly preferable 1 :N 2 1 to 8. Amount N 1 :N 2 1, N is < 9 1 And N 2 Mixed use, can adjust the volatilization speed, and can obviously improve the surface drying speed during sprayingThe amount N is used to ensure that the paint film achieves the optimal performance 1 :N 2 And the volatilization speed is kept balanced, so that the coating is favorable for the adhesion and toughness of a coating and the covering power of the pigment is improved.
A method for producing an environment-friendly fluorine-containing copolymer, comprising the steps of:
(1) Before polymerization, adding 100% of chain transfer agent into a polymerization vessel, adding 20% -100% of initiator into the polymerization vessel, adding 20% -100% of vinyl fluorine-containing monomer into the polymerization vessel, adding 20% -100% of vinyl non-fluorine monomer into the polymerization vessel, and adding 20% -100% of organic solvent into the polymerization vessel;
(2) Stirring and carrying out polymerization reaction, adding 80-0% of initiator into a polymerization container when polymerizing for h1 time, adding 60-0% of initiator into the polymerization container when polymerizing for h2 time, adding 40-0% of initiator into the polymerization container when polymerizing for h3 time, and adding the rest of initiator into the polymerization container when polymerizing for h4 time;
(3) Continuously adding the rest vinyl fluorine-containing monomer, vinyl non-fluorine monomer and organic solvent into a polymerization container until the reaction is finished;
(4) And (4) separating 40-100% of organic solvent from the fluorine-containing polymer obtained in the step (3) under reduced pressure, and simultaneously adding the same amount of environment-friendly solvent.
Preferably, the polyfluoro copolymer polymerization is carried out at a temperature of from 40 to 80 deg.C, preferably 70 deg.C.
Preferably, the fluorocopolymer is carried out at from 0.2 to 1.2MPa, preferably from 0.4 to 0.9MPa, particularly preferably from 0.4 to 0.6 MPa.
Preferably, the polymerization of the fluorocopolymer is carried out for a period of time ranging from 14 to 20 hours, preferably 16 hours.
Preferably, the fluorocopolymer is stirred at a rate of from 200 to 800rpm, preferably 400rpm.
Preferably, the reduced pressure in the step (4) is-0.07 to-0.09 MPa.
Due to the adoption of the technical scheme, the invention has the following beneficial effects:
the vinyl non-fluorine monomer comprises a vinyl non-fluorine monomer containing hydroxyl or alcohol group but not containing carboxyl, and the main purpose is that the monomer provides hydroxyl which reacts with NCO in curing agent isocyanate to form a compact net structure when the coating is made; the vinyl non-fluorine monomer containing carboxyl and no hydroxyl or alcohol group mainly aims at providing carboxyl by the monomer, and the carboxyl is favorable for wetting and dispersing the pigment and the filler when being prepared into the coating; one or more vinyl non-fluorine monomers containing neither carboxyl nor hydroxyl or alcohol group, mainly contains cyclohexyl to increase the solubility, transparency, adhesion and the like of the resin.
The invention can utilize the manufacturing method of part of the monomers to continuously feed to obtain the fluorine-containing copolymer which has low polymerization pressure, simple and easily controlled process, uniform and adjustable molecular weight distribution, can realize normal-temperature curing, and has excellent solvent resistance, water resistance, long-term weather resistance, gloss and the like.
The polymerization reaction is a gas-liquid reaction, the amount of the fed materials at the early stage is small, the concentration of the reactants is low, and the frequency of intermolecular collision can be controlled by adopting a continuous feeding mode and controlling the feeding speed, so that the molecular weight distribution and the molecular weight are controlled.
The organic solvent adopted in the invention is butyl acetate, which has good dissolving effect on resin, but has heavy smell and influences on body health, and the adopted environment-friendly solvent has the characteristics of excellent dissolving performance, low toxicity, low smell, high flash point, low steam pressure, high explosion lower limit in air and the like, and is an environment-friendly solvent capable of being biodegraded.
Detailed Description
The present invention will be described below by way of examples and comparative examples, but the present invention is not limited to the following examples.
Examples 1 to 5
Vacuumizing a 5L polymerization vessel equipped with a stirrer, replacing the polymerization vessel with nitrogen until the oxygen content is less than or equal to 10ppm, adding 100% of chain transfer agent into the polymerization vessel at a time, adding 100% of initiator into the polymerization vessel, adding 100% of vinyl fluorine-containing monomer into the polymerization vessel, adding 100% of vinyl non-fluorine monomer into the polymerization vessel, and adding 100% of organic solvent into the polymerization vessel. The polymerization temperature of the fluorine-containing copolymer is 70 ℃, and the polymerization time is 16h. The stirring rate was 400rpm.
The specific components are shown in table 1.
Table 1: examples 1-5 raw material components.
Example 6
To illustrate the effect of the present invention, inventive example 1 was continuously fed, and 100% chain transfer agent and 20% initiator were added to the polymerization vessel before polymerization; adding 20% vinyl fluoromonomer to a polymerization vessel; adding 20% of a vinyl non-fluorinated monomer to a polymerization vessel; to the polymerization vessel was added 20% organic solvent.
After 2h of polymerization, 20% of initiator was added to the polymerization vessel; at 4h of polymerization, 20% of initiator was added to the polymerization vessel; at 8h of polymerization, 20% initiator was added to the polymerization vessel; at 14h of polymerization, the remaining initiator was added to the polymerization vessel.
During polymerization, a mixed solution of 80% of vinyl fluorine-containing monomer, vinyl non-fluorine monomer and organic solvent is continuously added into a polymerization vessel until the reaction is finished.
The specific components are shown in table 2.
Table 2: example 6 raw material components.
Example 7
To illustrate the effect of the present invention, inventive example 5 was continuously fed, and 100% chain transfer agent and 20% initiator were added to the polymerization vessel prior to polymerization; adding 20% of a vinyl fluoromonomer to a polymerization vessel; adding 20% of a vinyl non-fluorine monomer to a polymerization vessel; to the polymerization vessel was added 20% organic solvent.
After 2h of polymerization, 20% of initiator was added to the polymerization vessel; at 4h of polymerization, 20% of initiator was added to the polymerization vessel; at 8h of polymerization, 20% initiator was added to the polymerization vessel; at 14h of polymerization, the remaining initiator was added to the polymerization vessel.
During polymerization, a mixed solution of 80% of vinyl fluorine-containing monomer, vinyl non-fluorine monomer and organic solvent is continuously added into a polymerization vessel until the reaction is finished.
The specific components are shown in table 3.
Table 3: example 7 raw material components.
The molecular weight was measured by gel permeation chromatography.
(1) And (3) drying: the sample is thoroughly dried to remove solvents and other impurities.
(2) Dissolving time: sufficient dissolution time is necessary to completely dissolve the sample in the solvent.
(3) Concentration: the concentration was taken as 0.3% mass fraction.
Note that: in preparing the solution, the sample solution may be agitated in order to increase the solubility of the sample, but cannot be sonicated to avoid molecular weight breakdown.
The yield is calculated by the formula:
the following evaluations were carried out using the resulting fluorocopolymers 1 to 7, and the results are shown in Table 4.
Table 4: EXAMPLES 1 to 7 evaluation tables for fluorocopolymer
| Detecting items | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 |
| Polymerization pressure | 0.71 | 0.83 | 0.60 | 0.69 | 0.88 | 0.42 | 0.48 |
| Molecular weight | 35000 | 37000 | 28000 | 43000 | 45000 | 34000 | 35000 |
| Molecular weight distribution | 3.8 | 3.7 | 3.5 | 3.5 | 3.7 | 2.9 | 2.9 |
| Yield (a% | 96.1 | 95.7 | 95.4 | 95.6 | 96.1 | 97.0 | 97.1 |
Examples 8 to 14
To illustrate the effects of the present invention, coating compositions (examples 8 to 10) were prepared from the fluorocopolymer in which part of the solvent was replaced in example 6, and coating compositions (examples 11 to 14) were prepared from the fluorocopolymer in which part of the solvent was replaced in example 7, by the following methods: 100g of fluorine-containing copolymer, 0.5g of dispersing agent, 0.5g of flatting agent, 0.5g of defoaming agent and 10g of isocyanate curing agent are uniformly dispersed and sprayed on a standard plate for removing oil and rust, and the performance of the standard plate is tested.
The surface drying time adopts a method B in GB/T1728-2020.
The paint film surface was slightly touched with a finger, and was slightly tacky, but no paint was stuck to the finger, i.e., the surface was considered dry.
The adhesion is tested by GB/T1720-2020.
The flexibility is tested by GB/T1731-2020.
Water resistance was tested using GB/T1733-1993.
The artificial accelerated aging is tested by GB/T1865-2009.
The specific components and test results are shown in table 5.
Table 5: compositions and test results for examples 8-14.
A-slight, A + heavy, A + + very heavy
The composition and the preparation method of the environment-friendly fluorine-containing copolymer have the advantages that the fluorine-containing copolymer with low polymerization pressure, simple and easily-controlled process, uniform and adjustable molecular weight distribution can be obtained by utilizing the preparation method of partial continuous monomer feeding, and the solvent used by the fluorine-containing copolymer prepared by the method is environment-friendly, can be cured at normal temperature, and has excellent solvent resistance, water resistance, long-term weather resistance, gloss and the like.
The above are only specific embodiments of the present invention, but the technical features of the present invention are not limited thereto. Any simple changes, equivalent substitutions or modifications based on the present invention to solve the same technical problems and achieve the same technical effects are all covered by the protection scope of the present invention.
Claims (10)
1. The environment-friendly fluorine-containing copolymer is characterized by comprising the following components in parts by mass:
2. the environmentally friendly fluorine-containing copolymer according to claim 1, wherein: the chain transfer agent is one or more of aliphatic mercaptan, dodecyl mercaptan and isopropanol.
3. The environmentally friendly fluorine-containing copolymer according to claim 1, wherein: the initiator is a peroxide initiator.
4. The environmentally friendly fluorine-containing copolymer according to claim 1, wherein: the vinyl fluorine-containing monomer is a monomer in which at least 1 hydrogen atom bonded to a carbon atom is replaced by a fluorine atom.
5. The environmentally friendly fluorine-containing copolymer according to claim 1, wherein: the vinyl non-fluorine monomer comprises one or more of a vinyl non-fluorine monomer containing a hydroxyl group or an alcohol group but not containing a carboxyl group, a vinyl non-fluorine monomer containing a carboxyl group but not containing a hydroxyl group or an alcohol group, and a vinyl non-fluorine monomer containing neither a carboxyl group nor a hydroxyl group or an alcohol group.
6. The environmentally friendly fluorine-containing copolymer according to claim 1, wherein: the organic solvent comprises one or more of butyl acetate, toluene, xylene and methyl isobutyl ketone.
7. The environmentally friendly fluorine-containing copolymer according to claim 1, wherein: the general formula of the environmental-friendly solvent is CH 3 O-CO-[(CH 2 ) n -CO-] m -O-CH 3 M is less than or equal to 1, n is less than or equal to 4.
8. The process for producing an environmentally friendly fluorocopolymer according to claim 1, which comprises the steps of:
(1) Before polymerization, adding 100% of chain transfer agent into a polymerization vessel, adding 20% -100% of initiator into the polymerization vessel, adding 20% -100% of vinyl fluorine-containing monomer into the polymerization vessel, adding 20% -100% of vinyl non-fluorine monomer into the polymerization vessel, and adding 20% -100% of organic solvent into the polymerization vessel;
(2) Stirring and carrying out polymerization reaction, adding 80-0% of initiator into a polymerization container when the polymerization is carried out for h1 time, adding 60-0% of initiator into the polymerization container when the polymerization is carried out for h2 time, adding 40-0% of initiator into the polymerization container when the polymerization is carried out for h3 time, and adding the rest of initiator into the polymerization container when the polymerization is carried out for h4 time;
(3) Continuously adding the rest vinyl fluorine-containing monomer, vinyl non-fluorine monomer and organic solvent into a polymerization container until the reaction is finished to obtain fluorine-containing copolymer;
(4) And (3) separating 40-100% of the organic solvent from the fluorine-containing polymer obtained in the step (3) under reduced pressure, and simultaneously adding an equal amount of environment-friendly solvent.
9. The method for producing the environmentally friendly fluorocopolymer according to claim 8, wherein: the polymerization time of the fluorine-containing copolymer is 14-20h, the polymerization temperature is 40-80 ℃, and the polymerization pressure is 0.2-1.2MPa.
10. The method for producing the environmentally friendly fluorocopolymer according to claim 8, wherein: the reduced pressure in the step (4) is-0.07 to-0.09 MPa. .
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