Fluorine-containing copolymer, process for producing the same, and use thereof

Abstract

The present application provides a fluorine-containing copolymer, which comprises a fluorine-containing olefin first monomer, a hydroxyalkyl vinyl ether second monomer and an alkyl vinyl ether third monomer; the fluorine-containing copolymer of the present application is suitable for preparing coatings, adhesives and coiled materials, and has excellent weather resistance, chemical corrosion resistance, high temperature and humidity resistance, yellowing resistance, mechanical strength and the like while achieving high flexibility.

Description

Technical Field

[0001] This application relates to the fields of adhesives, coatings and coils, and more specifically to a highly flexible fluorinated copolymer, a method for its preparation, and the application of the fluorinated copolymer in coatings, adhesives and coils. Background Technology

[0002] Fluorocarbon resin (FEVE) is a polymer with fluorine atoms on its main chain or side chains, obtained by copolymerizing various fluorine-containing monomers with some non-fluorine monomers. Microscopically, the fluorine atoms in FEVE form an almost complete cylindrical shell in a helical shape, tightly surrounding the main chain. Strong F-C bonds enclose weaker C-C bonds, making the polymer less susceptible to damage from external factors. Therefore, FEVE possesses excellent weather resistance, chemical stability, and mechanical strength. However, FEVE also has unresolved issues, such as its often poor flexibility. Extensive research has been conducted to address this problem, but all studies have failed; the resulting products still lack sufficient flexibility and may even significantly degrade the original weather resistance, chemical stability, and mechanical strength of the FEVE material.

[0003] Therefore, there is an urgent need to develop a new type of fluorocarbon resin that possesses high flexibility while also exhibiting excellent weather resistance, chemical stability, and mechanical strength, so as to enable the application of this material in fields such as coatings, adhesives, roll materials, and others. Summary of the Invention

[0004] In response to the above problems, the inventors of this application conducted in-depth research and successfully developed a fluorinated copolymer material, thereby effectively solving a long-standing problem in the prior art.

[0005] The first aspect of this application provides a fluorinated copolymer comprising copolymer units derived from monomers:

[0006] First monomer: The first monomer comprises at least one compound represented by Formula I:

[0007]

[0008] Where R 1 R 2 R 3 and R 4 Each is independently selected from fluorine, chlorine, bromine, iodine, C1-C 12 Alkyl, C1-C 12 Haloalkyl, C2-C 12 alkenyl, C2-C 12Haloalkenyl groups and combinations thereof, provided that the compound represented by Formula I contains at least one fluorine atom;

[0009] Second monomer: The second monomer comprises at least one compound represented by Formula II:

[0010]

[0011] Where R 5 Selected from: C1-C 16 Hydroxyalkyl, hydroxy-C3-C 16 Cycloalkyl, hydroxy-C6-C 16 Aryl, hydroxy-C6-C 16 Aryl alkyl; R 6 R 7 and R 8 Each is independently selected from hydrogen, fluorine, chlorine, bromine, iodine, C1-C 12 Alkyl, C1-C 12 Haloalkyl, C2-C 12 alkenyl, C2-C 12 Haloalkenes and combinations thereof;

[0012] Third monomer: The third monomer comprises at least one compound represented by Formula III:

[0013]

[0014] Where R 9 Selected from: C1-C 24 Alkyl, C3-C 24 cycloalkyl, C6-C 24 Aryl, C6-C 24 Aryl alkyl; R 10 R 11 and R 12 Each is independently selected from hydrogen, fluorine, chlorine, bromine, iodine, C1-C 12 Alkyl, C1-C 12 Haloalkyl, C2-C 12 alkenyl, C2-C 12 Haloalkenes and their combinations.

[0015] According to one embodiment of the first aspect of this application, the fluorinated copolymer does not contain copolymer units derived from vinyl esters.

[0016] According to another embodiment of the first aspect of this application, the first monomer is selected from one or more of the following: tetrafluoroethylene, trifluorochloroethylene, difluorodichloroethylene, trifluorochloroethylene, perfluoropropylene, perfluorobutene, perfluoropentene, perfluorohexene, perfluoroheptene, perfluorooctene, perfluorononene, perfluorodecene, perfluoroundecene, perfluorododecene, fluorochloropropylene, fluorochlorobutene, fluorochloropentene, fluorochlorohexene, fluorochloroheptene, fluorochlorooctene, fluorochlorononene, fluorochlorodecene, fluorochloroundecene, and fluorochlorododecene. According to another embodiment of the first aspect of this application, the content of the first monomer is 40-60 mol% based on a total molar amount of 100 mol% of all monomers used to form the fluorinated copolymer.

[0017] According to another embodiment of the first aspect of this application, the second monomer is selected from one or more of the following: hydroxymethyl vinyl ether, hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, hydroxypentyl vinyl ether, hydroxyhexyl vinyl ether, hydroxydecyl vinyl ether, hydroxydodecyl vinyl ether, hydroxyhexadecyl vinyl ether, hydroxycyclopropyl vinyl ether, hydroxycyclobutyl vinyl ether, hydroxycyclopentyl vinyl ether, and hydroxycyclohexyl vinyl ether. According to another embodiment of the first aspect of this application, the content of the second monomer is 3-30 mol%, based on a total molar amount of 100 mol% of all monomers used to form the fluorinated copolymer.

[0018] According to another embodiment of the first aspect of this application, the third monomer is selected from one or more of the following: ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, pentyl vinyl ether, hexyl vinyl ether, heptyl vinyl ether, octyl vinyl ether, nonyl vinyl ether, decyl vinyl ether, dodecyl vinyl ether, tetradecyl vinyl ether, hexadecyl vinyl ether, octadecyl vinyl ether, dodecyl vinyl ether, cyclopropyl vinyl ether, cyclobutyl vinyl ether, cyclopentyl vinyl ether, and cyclohexyl vinyl ether. According to another embodiment of the first aspect of this application, the content of the third monomer is 10-50 mol%, based on a total molar amount of 100 mol% of all monomers used to form the fluorinated copolymer.

[0019] According to another embodiment of the first aspect of this application, the third monomer comprises a compound represented by formula IIIa and optionally a compound represented by formula IIIb.

[0020]

[0021] Where R 9a Selected from: C1-C8 alkyl, C3-C8 cycloalkyl, C6-C8 aryl, C6-C8 aralkyl;

[0022] R 9bSelected from: C9-C 24 Alkyl, C9-C 24 cycloalkyl, C9-C 24 Aryl, C9-C 24 Aryl alkyl groups;

[0023] R 10 R 11 and R 12 Each is independently selected from hydrogen, fluorine, chlorine, bromine, iodine, C1-C 12 Alkyl, C1-C 12 Haloalkyl, C2-C 12 alkenyl, C2-C 12 Halogenated alkenyl groups and combinations thereof. According to another embodiment of the first aspect of this application, the molar ratio of the compound represented by formula IIIa to the compound represented by formula IIIb is 10:1 to 1:1.

[0024] According to another embodiment of the first aspect of this application, the number-average molecular weight Mn of the fluorinated copolymer is 5,000 to 50,000.

[0025] A second aspect of this application provides a coating composition comprising the fluorinated copolymer of this application. A second aspect of this application also provides an adhesive composition comprising the fluorinated copolymer of this application. According to one embodiment of the second aspect of this application, based on 100% by weight of the total weight of the coating composition or adhesive composition, the coating composition or adhesive composition comprises: 50-65% by weight of the fluorinated copolymer of any one of claims 1-7; 0-50% by weight of one or more optional additives; and the balance being a solvent.

[0026] A third aspect of this application provides a roll material comprising the coating composition of this application.

[0027] A fourth aspect of this application provides a method for preparing the fluorinated copolymer of the present invention, the method comprising copolymerizing the first monomer, the second monomer, and the third monomer in the presence of an initiator and a solvent to form the fluorinated copolymer. Attached Figure Description

[0028] The following paragraphs discuss various embodiments of this application in conjunction with the accompanying drawings. However, it should be noted that the embodiments shown in the drawings and described in detail below are merely some preferred embodiments of this application, and the scope of protection of this application is defined by the claims, and not limited to these preferred embodiments. Furthermore, for clarity, the various components shown in the accompanying drawings are not drawn to scale.

[0029] Figure 1 The illustration shows a comparison of UV aging results according to one embodiment of the present invention and a comparative embodiment. Detailed Implementation

[0030] The “range” disclosed in this document takes the form of a lower limit and an upper limit. It can be one or more lower limits and one or more upper limits, respectively. A given range is defined by selecting a lower limit and an upper limit. The selected lower and upper limits define the boundaries of the particular range. All ranges that can be defined in this way are inclusive and composable; that is, any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a specific parameter, it is also expected that ranges of 60-110 and 80-120 are also included. Furthermore, if the minimum range values ​​are listed as 1 and 2, and if the maximum range values ​​are listed as 3, 4, and 5, then the following ranges are all expected: 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5.

[0031] In this application, unless otherwise stated, the numerical range "ab" is a shortened representation of any combination of real numbers from a to b, where a and b are real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" have been listed in this document, and "0-5" is simply a shortened representation of these numerical combinations.

[0032] Unless otherwise specified in this application, all embodiments and preferred embodiments mentioned herein can be combined to form new technical solutions.

[0033] Unless otherwise specified, all technical features and preferred features mentioned herein can be combined to form new technical solutions.

[0034] In this application, unless otherwise specified, the term "comprising" as used herein can be either open-ended or closed-ended. For example, "comprising" may mean that it may also include other components not listed, or it may only include the listed components.

[0035] In this application, the term "polymeric structural unit / copolymeric structural unit derived from a monomer" refers to a structural unit formed by the monomer through an addition polymerization reaction of carbon-carbon double bonds in its molecule, which is part of the copolymer backbone. The original composition, substituents, and structure of the monomer are retained in the copolymer structural unit formed therefrom, but may also be appropriately changed through chemical reactions.

[0036] The fluorinated copolymer of this application comprises copolymer units derived from a first monomer, a second monomer, and a third monomer.

[0037] According to one embodiment of this application, the first monomer comprises at least one compound of formula I:

[0038]

[0039] Where R 1 R 2 R 3 and R 4 Each is independently selected from fluorine, chlorine, bromine, iodine, C1-C 12 Alkyl, C1-C 12 Haloalkyl, C2-C 12 alkenyl, C2-C 12 Haloalkenyl groups and combinations thereof; for example, R 1 R 2 R 3 and R 4 Each is independently selected from fluorine, chlorine, bromine, iodine, C1-C 10 Alkyl, C1-C 10 Haloalkyl, C2-C 10 alkenyl, C2-C 10 Haloalkenyl groups and combinations thereof; or R 1 R 2 R 3 and R 4 Each is independently selected from fluorine, chlorine, bromine, iodine, C1-C8 alkyl, C1-C8 haloalkyl, C2-C8 alkenyl, C2-C8 haloalkenyl, and combinations thereof; or R 1 R 2 R 3 and R 4 Each is independently selected from fluorine, chlorine, bromine, iodine, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, and combinations thereof; or R 1 R 2 R 3 and R 4 Each is independently selected from fluorine, chlorine, bromine, iodine, C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, C2-C4 haloalkenyl, and combinations thereof. The prerequisite is that the compound represented by Formula I contains at least one fluorine atom; for example, the compound represented by Formula I may contain one, two, three, four, five, six, seven, eight, nine, ten, or more fluorine atoms.

[0040] In the context of this application, when a group (e.g., alkyl, alkenyl, cycloalkyl, aryl, aralkyl, etc.) is described as "halogenated", it means that at least one to all of the hydrogen atoms in the group that are attached to a carbon atom, for example, 10-100%, or 20-90%, or 30-80%, or 40-70%, or 50-60%, are replaced by halogen atoms, which may include fluorine, chlorine, bromine, iodine, or combinations thereof.

[0041] According to a preferred embodiment of this application, the first monomer is selected from one or more of the following: tetrafluoroethylene, trifluorochloroethylene, difluorodichloroethylene, trifluorochloroethylene, perfluoropropylene, perfluorobutene, perfluoropentene, perfluorohexene, perfluoroheptene, perfluorooctene, perfluorononene, perfluorodecene, perfluoroundecene, perfluorododecene, fluorochloropropylene, fluorochlorobutene, fluorochloropentene, fluorochlorohexene, fluorochloroheptene, fluorochlorooctene, fluorochlorononene, fluorochlorodecene, fluorochloroundecene, and fluorochlorododecene. According to a specific embodiment of this application, the first monomer is tetrafluoroethylene, trifluorochloroethylene, or a combination thereof.

[0042] According to one embodiment of this application, with the total molar amount of all monomers used to form the fluorinated copolymer being 100 mol%, the content of the first monomer is 40-60 mol%, for example, 42-58 mol%, or 44-57 mol%, or 45-56 mol%, or 48-55 mol%, or 50-54 mol%, or 52-52 mol%, or within a range of values ​​obtained by combining any two of the above endpoints.

[0043] According to one embodiment of this application, the second monomer comprises at least one compound represented by Formula II:

[0044]

[0045] Where R 5 Selected from: C1-C 16 Hydroxyalkyl, hydroxy-C3-C 16 Cycloalkyl, hydroxy-C6-C 16 Aryl, hydroxy-C6-C 16 Aryl alkyl groups; for example, R 5 Selected from: C1-C 14 Hydroxyalkyl, hydroxy-C3-C 14 Cycloalkyl, hydroxy-C6-C 14 Aryl, hydroxy-C6-C 14 Aryl alkyl; or R 5 Selected from: C1-C 12 Hydroxyalkyl, hydroxy-C3-C 12 Cycloalkyl, hydroxy-C6-C12 Aryl, hydroxy-C6-C 12 Aryl alkyl; or R 5 Selected from: C1-C 10 Hydroxyalkyl, hydroxy-C3-C 10 Cycloalkyl, hydroxy-C6-C 10 Aryl, hydroxy-C6-C 10 Aryl alkyl; or R 5 Selected from: C1-C8 hydroxyalkyl, hydroxy-C3-C8 cycloalkyl, hydroxy-C6-C8 aryl, hydroxy-C6-C8 aralkyl. According to one embodiment of this application, the R... 5 It contains one, two, three, four, five, six, seven, or eight hydroxyl groups. R 6 R 7 and R 8 Each is independently selected from hydrogen, fluorine, chlorine, bromine, iodine, C1-C 12 Alkyl, C1-C 12 Haloalkyl, C2-C 12 alkenyl, C2-C 12 Haloalkenyl groups and combinations thereof; for example, R 6 R 7 and R 8 Each is independently selected from hydrogen, fluorine, chlorine, bromine, iodine, C1-C 10 Alkyl, C1-C 10 Haloalkyl, C2-C 10 alkenyl, C2-C 10 Haloalkenyl groups and combinations thereof; or R 6 R 7 and R 8 Each is independently selected from hydrogen, fluorine, chlorine, bromine, iodine, C1-C8 alkyl, C1-C8 haloalkyl, C2-C8 alkenyl, C2-C8 haloalkenyl, and combinations thereof; or R 6 R 7 and R 8 Each monomer is independently selected from hydrogen, fluorine, chlorine, bromine, iodine, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, and combinations thereof. According to one specific embodiment of this application, the second monomer is selected from one or more of the following: hydroxymethyl vinyl ether, hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, hydroxypentyl vinyl ether, hydroxyhexyl vinyl ether, hydroxydecyl vinyl ether, hydroxydodecyl vinyl ether, hydroxyhexadecyl vinyl ether, hydroxycyclopropyl vinyl ether, hydroxycyclobutyl vinyl ether, hydroxycyclopentyl vinyl ether, and hydroxycyclohexyl vinyl ether. According to one specific embodiment of this application, the second monomer is hydroxybutyl vinyl ether.

[0046] According to one embodiment of this application, with the total molar amount of all monomers used to form the fluorinated copolymer being 100 mol%, the content of the second monomer is 3-30, for example 4-28 mol%, or 5-26 mol%, or 6-25 mol%, or 8-22 mol%, or 10-20 mol%, or 12-18 mol%, or 15-16 mol%, or within the range of values ​​obtained by combining any two of the above endpoints.

[0047] According to one embodiment of this application, the third monomer comprises at least one compound represented by Formula III:

[0048]

[0049] Where R 9 Selected from: C1-C 24 Alkyl, C3-C 24 cycloalkyl, C6-C 24 Aryl, C6-C 24 Aryl alkyl groups; for example, R 9 Selected from: C1-C 22 Alkyl, C3-C 22 cycloalkyl, C6-C 22 Aryl, C6-C 22 Aryl alkyl; or R 9 Selected from: C1-C 18 Alkyl, C3-C 18 cycloalkyl, C6-C 18 Aryl, C6-C 18 Aryl alkyl; or R 9 Selected from: C1-C 16 Alkyl, C3-C 16 cycloalkyl, C6-C 16 Aryl, C6-C 16 Aryl alkyl; or R 9 Selected from: C1-C 12 Alkyl, C3-C 12 cycloalkyl, C6-C 12 Aryl, C6-C 12 Aryl alkyl; R 9 Selected from: C1-C8 alkyl, C3-C8 cycloalkyl, C6-C8 aryl, C6-C8 aralkyl; or R 9 Selected from: C1-C6 alkyl, C3-C6 cycloalkyl, C6-C8 aryl, C6-C8 aralkyl. R 10 R 11 and R 12 Each is independently selected from hydrogen, fluorine, chlorine, bromine, iodine, C1-C 12 Alkyl, C1-C 12 Haloalkyl, C2-C12 alkenyl, C2-C 12 Haloalkenyl groups and combinations thereof, or R 10 R 11 and R 12 Each is independently selected from hydrogen, fluorine, chlorine, bromine, iodine, C1-C 10 Alkyl, C1-C 10 Haloalkyl, C2-C 10 alkenyl, C2-C 10 Haloalkenyl groups and combinations thereof, or R 10 R 11 and R 12 Each is independently selected from hydrogen, fluorine, chlorine, bromine, iodine, C1-C8 alkyl, C1-C8 haloalkyl, C2-C8 alkenyl, C2-C8 haloalkenyl, and combinations thereof, or R 10 R 11 and R 12 Each is independently selected from hydrogen, fluorine, chlorine, bromine, iodine, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, and combinations thereof, or R 10 R 11 and R 12 Each is independently selected from hydrogen, fluorine, chlorine, bromine, iodine, C1-C3 alkyl, C1-C3 haloalkyl, C2-C3 alkenyl, C2-C3 haloalkenyl, and combinations thereof.

[0050] According to one embodiment of this application, with the total molar amount of all monomers used to form the fluorinated copolymer being 100 mol%, the content of the third monomer is 10-50, for example 12-48 mol%, or 15-45 mol%, or 18-42 mol%, or 20-40 mol%, or 22-38 mol%, or 25-36 mol%, or 28-35 mol%, or 30-32 mol%, or within a numerical range obtained by combining any two of the above endpoints.

[0051] According to one embodiment of this application, the third monomer includes compounds represented by formula IIIa and formula IIIb.

[0052]

[0053] Where R 9a Selected from: C1-C8 alkyl, C3-C8 cycloalkyl, C6-C8 aryl, C6-C8 aralkyl; for example, R 9a Selected from: C1-C6 alkyl, C3-C6 cycloalkyl, C6-C7 aryl, C6-C7 aralkyl; R 9b Selected from: C9-C 24 Alkyl, C9-C 24cycloalkyl, C9-C 24 Aryl, C9-C 24 Aryl alkyl groups; for example, R 9b Selected from: C9-C 20 Alkyl, C9-C 20 cycloalkyl, C9-C 20 Aryl, C9-C 20 Aryl alkyl; or R 9b Selected from: C9-C 16 Alkyl, C9-C 16 cycloalkyl, C9-C 16 Aryl, C9-C 16 Aryl alkyl; or R 9b Selected from: C9-C 12 Alkyl, C9-C 12 cycloalkyl, C9-C 12 Aryl, C9-C 12 Aryl alkyl; R 10 R 11 and R 12 Each is as described above. According to one embodiment of this application, the molar ratio of the compound represented by Formula IIIa to the compound represented by Formula IIIb is 10:1 to 1:1, for example, 9:1 to 2:1, or 8:1 to 3:1, or 7:1 to 4:1, or 6:1 to 5:1, or the ratio of the two is within the numerical range obtained by combining any two of the above end values.

[0054] According to another embodiment of this application, the third monomer contains only the compound shown in formula IIIa, but not the compound shown in formula IIIb.

[0055] According to one embodiment of this application, the third monomer is selected from one or more of the following: ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, pentyl vinyl ether, hexyl vinyl ether, heptyl vinyl ether, octyl vinyl ether, nonyl vinyl ether, decyl vinyl ether, dodecyl vinyl ether, tetradecyl vinyl ether, hexadecyl vinyl ether, octadecyl vinyl ether, docosyl vinyl ether, cyclopropyl vinyl ether, cyclobutyl vinyl ether, cyclopentyl vinyl ether, and cyclohexyl vinyl ether. According to a preferred embodiment of this application, the third monomer comprises a combination of shorter-chain alkyl vinyl ethers (e.g., one or more of ethyl vinyl ether, propyl vinyl ether, and butyl vinyl ether) and longer-chain alkyl vinyl ethers (e.g., one or more of hexadecyl vinyl ether, dodecyl vinyl ether, and decyl vinyl ether). According to another preferred embodiment of this application, the third monomer comprises only shorter-chain alkyl vinyl ethers (e.g., one or more of ethyl vinyl ether, propyl vinyl ether, and butyl vinyl ether), and does not contain longer-chain alkyl vinyl ethers (e.g., one or more of hexadecyl vinyl ether, dodecyl vinyl ether, and decyl vinyl ether).

[0056] According to one embodiment of this application, the fluorinated copolymer does not contain monomers derived from vinyl esters. In this application, "vinyl ester" refers to an ester compound whose molecular structure can be viewed as CH2=CH-OH esterified with any one or more carboxylic acids; however, "vinyl ester" does not necessarily have to be prepared by esterification of vinyl alcohol with carboxylic acids as described above, but can be prepared by any suitable method. According to another embodiment of this application, the fluorinated copolymer does not contain any monomers having ester groups.

[0057] According to one embodiment of this application, the number-average molecular weight Mn of the fluorinated copolymer is 5000-50,000, for example, it can be 8000-45000, or 9000-40000, or 10000-35000, or 11000-32000, or 12000-30000, or 13000-25000, or 14000-22000, or 15000-20000, or 16000-18000, or it can be within the range of any combination of the above two end values. The number-average molecular weight can be characterized using techniques known in the art, such as end-group analysis, membrane permeation, etc., and the molecular weight of the copolymer can be detected using a commercial molecular weight analyzer according to the instrument manual or standard methods.

[0058] This application provides a method for preparing the fluorinated copolymer, the method comprising copolymerizing the first monomer, the second monomer, and the third monomer in the presence of an initiator, a stabilizer, and a solvent to form the fluorinated copolymer.

[0059] According to one embodiment of this application, the solvent is water or an organic solvent, examples of which may include benzene, toluene, xylene, cyclohexane, ethyl acetate, etc. The polymerization reaction is a solution polymerization reaction, for example, based on the total mass of all materials in the polymerization reaction system, the solid content of the polymerization reaction system (i.e., the ratio of the total weight of components other than the solvent to the total weight of all materials in the polymerization reaction system) is 10-80% by weight, for example 20-70% by weight, or 30-60% by weight, or 40-55% by weight, or 45-50% by weight.

[0060] According to one embodiment of this application, the initiator used for the polymerization reaction can be various peroxide-based initiators known in the art, such as succinic acid peroxide, ammonium persulfate, hydrogen peroxide, tert-butyl hydrogen peroxide, potassium persulfate, benzoyl peroxide, tert-butyl peroxide, methyl ethyl ketone peroxide, tert-butyl peroxypentanoate, etc. For example, based on the total mass of all materials in the polymerization reaction system, the content of the initiator can be 0.01-10% by weight, for example, 0.02-9% by weight, or 0.04-8% by weight, or 0.05-7% by weight, or 0.08-6% by weight, or 0.1-5% by weight, or 0.2-4% by weight, or 0.3-3% by weight, or 0.5-2% by weight, or 0.8-1.5% by weight, or 1-1.2% by weight, or within a numerical range obtained by combining any two of the above endpoints.

[0061] According to another embodiment of this application, one or more other components, such as stabilizers, may be used in the polymerization reaction. A specific example of a stabilizer is a hindered amine light stabilizer, such as bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate. Another example of a stabilizer includes stabilizers used to improve the stability of the reaction system, such as paraffin wax, resin microspheres, etc. When a stabilizer is included in the polymerization reaction system, the content of the stabilizer, based on the total mass of all materials in the polymerization reaction system, may be 0.01-10% by weight, for example, 0.05-9% by weight, or 0.1-8% by weight, or 0.5-7% by weight, or 0.8-6% by weight, or 1-5% by weight, or 1.5-4% by weight, or 2-3% by weight, or may be within a numerical range obtained by combining any two of the above endpoints.

[0062] According to one embodiment of this application, the polymerization reaction can be carried out in air or an inert atmosphere, such as in an air atmosphere or a nitrogen atmosphere. According to one embodiment of this application, the polymerization temperature is 30-100°C, or 40-90°C, or 50-80°C, or 50-70°C, or 50-60°C, or 50-55°C, or a value range obtained by combining any two of the above extreme values. The duration of the polymerization reaction can be 0.5-100 hours, for example 1-90 hours, or 2-80 hours, or 3-60 hours, or 4-50 hours, or 5-40 hours, or 6-24 hours, or 7-12 hours, or 8-10 hours, or a value range obtained by combining any two of the above extreme values.

[0063] According to one embodiment of this application, the preparation of the fluorinated copolymer of this application can be carried out in the following manner: first, a solvent is added to the reactor, at least a portion of the comonomer is added to the reactor, and optionally an auxiliary agent (e.g., a stabilizer) is added to the reactor, the temperature is raised to the reaction temperature, and then an initiator is added to the reactor (the initiator can be added all at once, or added continuously or intermittently during the subsequent polymerization reaction), and subsequent comonomers are added as the reaction proceeds, so that the reaction continues for the time described above until the reaction is completed.

[0064] According to another embodiment of this application, after the polymerization reaction is completed, the polymerization product can be post-processed, which may include heating and concentration (removing solvent) and filtration (removing impurities).

[0065] According to some embodiments of this application, the copolymers of this application can be used in adhesives or coatings. According to one embodiment of this application, the adhesive composition or coating composition comprises, based on 100% by weight of the total composition:

[0066] 50-65% by weight of the fluorinated copolymer of this application;

[0067] 0-50% by weight of one or more optional additives; and

[0068] Optional solvent.

[0069] According to another embodiment of this application, in addition to the copolymer of this application, the adhesive or coating may also contain other additives as needed. Examples of additives that can be used in the adhesive of this application may include one or more of the following: diluents, lubricants, heat stabilizers, UV stabilizers, antioxidants, processing aids, dispersants, compatibilizers, coupling agents, tackifiers, fillers, impact modifiers, flame retardants, antistatic agents, conductive agents, pigments, colorants, plasticizers, processing aid oils, antibacterial agents, etc.

[0070] According to another embodiment of this application, the solvent used for the adhesive or coating may include one or more of the following: water, aliphatic hydrocarbons, aromatic hydrocarbons, alcohols, ketones, esters, alcohol ethers, etc.

[0071] Another embodiment of this application provides a roll material that can be prepared using the fluorinated copolymer of the present invention, or may include a substrate and an adhesive layer or coating layer disposed on one or both surfaces of the substrate, the adhesive layer or coating layer being formed using the adhesive composition or coating composition containing the fluorinated copolymer described above.

[0072] The fluorinated copolymers of the present invention, as well as coatings, adhesives and roll materials using the fluorinated copolymers, can effectively achieve high flexibility that has never been achieved by the prior art, and at the same time also have excellent weather resistance, chemical corrosion resistance, high temperature and high humidity resistance, yellowing resistance, and mechanical strength.

[0073] The present application is described below by way of specific embodiments, the purpose of which is to provide a better understanding of the content of the present application. It should be understood that these embodiments are merely illustrative and not restrictive. The reagents used in the embodiments, unless otherwise stated, are commercially available. The methods and conditions used in the embodiments, unless otherwise specified, are conventional methods and conditions.

[0074] Example

[0075] In the following embodiments, the copolymers of the present invention were prepared and their properties were compared with those of conventional copolymer materials of the prior art. The following embodiments are merely specific examples listed in this application, but the technical features of this application are not limited thereto. Any simple changes, equivalent substitutions, or other modifications made based on this application to solve essentially the same technical problem and achieve essentially the same technical effect are covered within the scope of protection of this application.

[0076] In the following examples, vinyl butyrate was purchased from Chongqing Chemical Industry Research Institute, tert-butyl peroxypentanoate PV-75 was purchased from Changshu Riyou Chemical Co., Ltd., trichlorofluoroethylene was from Changshu Sanai Fuzhonghao Chemical Co., Ltd., ethyl vinyl ether, decyl vinyl ether, hexadecyl vinyl ether, and hydroxybutyl vinyl ether were purchased from Xinjing Chemical Co., Ltd., stabilizer 292, solvent xylene, CAB381-0.5, PMA, BAC, 6900-20X, defoamer, DBE, NBA, 303, Deqian 432, defoamer, titanium dioxide, and aluminum paste were purchased from Akzo Corporation.

[0077] Example 1

[0078] In this embodiment, the fluorinated copolymer of this application was synthesized according to the following steps:

[0079] Add the components shown in Table 1 below to a 5000ml stainless steel autoclave equipped with a stirrer:

[0080] Table 1: Polymerization reaction raw materials used in Example 1

[0081]

[0082] 232g of ethyl vinyl ether, 216g of hydroxybutyl vinyl ether, and 212g of decyl vinyl ether were mixed to form a monomer mixture. Solvent, 80g of trifluorochloroethylene, and a stabilizer were added to the reactor. The temperature inside the reactor was raised to 54°C, and the initiator was added all at once to begin the polymerization reaction. The temperature inside the reactor was maintained at 54°C, and the monomer mixture and the remaining 680g of trifluorochloroethylene were continuously added over a 4-hour period. After the monomers were completely added, the reaction continued. The polymerization reaction was terminated after a total reaction time of 8 hours to obtain the FEVE resin semi-finished product.

[0083] The semi-finished product is transferred to a processing vessel, heated and concentrated to a solid content of 50 wt%. The material is then filtered to remove impurities, yielding a colorless and transparent product, denoted as fluorinated copolymer 1.

[0084] The viscosity of the fluorinated copolymer 1 was measured by a rotational viscometer; the acid value and hydroxyl value of the fluorinated copolymer 1 were measured by titration; the fluorine content of the fluorinated copolymer 1 was measured by combustion; the number-average molecular weight and D value of the fluorinated copolymer 1 were measured by GPC; the Tg of the fluorinated copolymer 1 was measured by DSC; and the breaking productivity of the fluorinated copolymer 1 was measured by a universal tensile testing machine.

[0085] The test results of the fluorinated copolymer 1 are summarized in Table 2 below.

[0086] Table 2: Characterization properties of fluorinated copolymer 1:

[0087] Finished product solid content (50wt%) 51.09 Appearance Colorless and transparent Viscosity (mPa·s) 920 Acid value (mgKOH / g-polymer) 1.42 Hydroxyl value (mgKOH / g-polymer) 56.77 Fluorine content (F wt%) 26.20 Mn(g / mol) 16182 D 2.18 Inflection point Tg (°C) 13.98 Elongation at break % 159

[0088] Using the fluorinated copolymer 1, coatings were prepared according to the formulations described in Table 3:

[0089] Table 3: Coating Formulations (Contents in the table are in parts by weight)

[0090] Fluorinated copolymer 1 65 copies CAB381-0.5 (25%) 17 copies PMA 5 copies 6900-20X 0.7 copies Deqian 432 0.2 copies Defoamer 0.1 copies Aluminum paste 12 copies

[0091] Example 2

[0092] In this embodiment, the fluorinated copolymer of this application was synthesized according to the following steps:

[0093] Add the components shown in Table 4 below to a 5000ml stainless steel autoclave equipped with a stirrer:

[0094] Table 4: Polymerization reaction raw materials used in Example 2

[0095]

[0096] 240g of ethyl vinyl ether, 216g of hydroxybutyl vinyl ether, and 150g of decyl vinyl ether were mixed to form a monomer mixture. Solvent, 80g of trifluorochloroethylene, and a stabilizer were added to the reactor. The temperature inside the reactor was raised to 54°C, and the initiator was added all at once to begin the polymerization reaction. The temperature inside the reactor was maintained at 54°C, and the monomer mixture and the remaining 680g of trifluorochloroethylene were continuously added over a 4-hour period. After the monomers were completely added, the reaction continued. The polymerization reaction was terminated after a total reaction time of 8 hours to obtain the FEVE resin semi-finished product.

[0097] The semi-finished product is transferred to a processing vessel, heated and concentrated to a solid content of 50 wt%. The material is then filtered to remove impurities, yielding a colorless and transparent product, denoted as fluorinated copolymer 2.

[0098] The test results of the fluorinated copolymer 2 are summarized in Table 5 below.

[0099] Table 5: Characterization properties of fluorinated copolymer 2:

[0100] Finished product solid content (50wt%) 50.63 Appearance Colorless and transparent Viscosity (mPa·s) 896 Acid value (mgKOH / g-polymer) 1.62 Hydroxyl value (mgKOH / g-polymer) 58.32 Fluorine content (F wt%) 27.10 Mn(g / mol) 17963 D 2.62 Inflection point Tg (°C) 14.20 Elongation at break % 169

[0101] Using the fluorinated copolymer 2, coatings were prepared according to the formulations described in Table 6:

[0102] Table 6: Coating Formulations (Contents in the table are in parts by weight)

[0103] Fluorinated copolymer 2 65 copies CAB381-0.5 (25%) 17 copies PMA 5 copies 6900-20X 0.7 copies Deqian 432 0.2 copies Defoamer 0.1 copies Aluminum paste 12 copies

[0104] Example 3

[0105] In this embodiment, the fluorinated copolymer of this application was synthesized according to the following steps:

[0106] Add the components shown in Table 7 below to a 5000ml stainless steel autoclave equipped with a stirrer:

[0107] Table 7: Polymerization reaction raw materials used in Example 3

[0108]

[0109] 232g of ethyl vinyl ether, 216g of hydroxybutyl vinyl ether, and 212g of decyl vinyl ether were mixed to form a monomer mixture. Solvent, 60g of tetrafluoroethylene, and a stabilizer were added to the reactor. The temperature inside the reactor was raised to 54°C, and the initiator was added all at once to begin the polymerization reaction. The temperature inside the reactor was maintained at 54°C, and the monomer mixture and the remaining 590g of tetrafluoroethylene were continuously added over a 4-hour period. After the monomers were completely added, the reaction continued. The polymerization reaction was terminated after a total reaction time of 8 hours to obtain the FEVE resin semi-finished product.

[0110] The semi-finished product was transferred to a processing vessel, heated, and concentrated until the solid content of the material was 50 wt%. The material was then filtered to remove impurities, yielding a colorless and transparent product, designated as fluorinated copolymer 3. The test results for fluorinated copolymer 3 are summarized in Table 8 below.

[0111] Table 8: Characterization properties of fluorinated copolymer 3:

[0112] Finished product solid content (50wt%) 52.35 Appearance Colorless and transparent Viscosity (mPa·s) 975 Acid value (mgKOH / g-polymer) 1.56 Hydroxyl value (mgKOH / g-polymer) 58.71 Fluorine content (F wt%) 29.20 Mn(g / mol) 13196 D 1.86 Inflection point Tg (°C) 12.39 Elongation at break % 194

[0113] Using the fluorinated copolymer 3, coatings were prepared according to the formulations described in Table 9:

[0114] Table 9: Coating Formulations (Contents in the table are in parts by weight)

[0115] Fluorinated copolymer 3 65 copies CAB381-0.5 (25%) 17 copies PMA 5 copies 6900-20X 0.7 copies Deqian 432 0.2 copies Defoamer 0.1 copies Aluminum paste 12 copies

[0116] Example 4

[0117] In this embodiment, the fluorinated copolymer of this application was synthesized according to the following steps:

[0118] Add the components shown in Table 10 below to a 5000ml stainless steel autoclave equipped with a stirrer:

[0119] Table 10: Polymerization reaction raw materials used in Example 4

[0120]

[0121]

[0122] 232g of ethyl vinyl ether, 216g of hydroxybutyl vinyl ether, and 300g of hexadecyl vinyl ether were mixed to form a monomer mixture. Solvent, 80g of trifluorochloroethylene, and a stabilizer were added to the reactor. The temperature inside the reactor was raised to 54°C, and the initiator was added all at once to begin the polymerization reaction. The temperature inside the reactor was maintained at 54°C, and the monomer mixture and the remaining 680g of trifluorochloroethylene were continuously added over a 4-hour period. After the monomers were completely added, the reaction continued. The polymerization reaction was terminated after a total reaction time of 8 hours to obtain a FEVE resin semi-finished product.

[0123] The semi-finished product is transferred to a processing vessel, heated and concentrated to a solid content of 50 wt%. The material is then filtered to remove impurities, yielding a colorless and transparent product, denoted as fluorinated copolymer 4.

[0124] The test results of the fluorinated copolymer 4 are summarized in Table 11 below.

[0125] Table 11: Characterization properties of fluorinated copolymer 4:

[0126] Finished product solid content (50wt%) 50.30 Appearance Colorless and transparent Viscosity (mPa·s) 719 Acid value (mgKOH / g-polymer) 1.22 Hydroxyl value (mgKOH / g-polymer) 48.28 Fluorine content (F wt%) 26.50 Mn(g / mol) 16271 D 2.2 Inflection point Tg (°C) 13.70 Elongation at break % 156

[0127] Using the fluorinated copolymer 4, coatings were prepared according to the formulations described in Table 12:

[0128] Table 12: Coating Formulations (Contents in the table are in parts by weight)

[0129] Fluorinated copolymer 4 50 copies PMA 10 copies BAC 3.3 copies 6900-20X 0.6 copies Defoamer 0.1 copies DBE 2 copies NBA 2 copies 303 7 copies Titanium dioxide 25 copies

[0130] Example 5

[0131] In this embodiment, the fluorinated copolymer of this application was synthesized according to the following steps:

[0132] Add the components shown in Table 13 below to a 5000ml stainless steel autoclave equipped with a stirrer:

[0133] Table 13: Polymerization reaction raw materials used in Example 5

[0134]

[0135] 252g of ethyl vinyl ether, 216g of hydroxybutyl vinyl ether, and 150g of hexadecyl vinyl ether were mixed to form a monomer mixture. Solvent, 80g of trifluorochloroethylene, and a stabilizer were added to the reactor. The temperature inside the reactor was raised to 54°C, and the initiator was added all at once to begin the polymerization reaction. The temperature inside the reactor was maintained at 54°C, and the monomer mixture and the remaining 760g of trifluorochloroethylene were continuously added over a 4-hour period. After the monomers were completely added, the reaction continued. The polymerization reaction was terminated after a total reaction time of 8 hours to obtain the FEVE resin semi-finished product.

[0136] The semi-finished product is transferred to a processing vessel, heated and concentrated to a solid content of 50 wt%. The material is then filtered to remove impurities, yielding a colorless and transparent product, denoted as fluorinated copolymer 5.

[0137] The test results of the fluorinated copolymer 5 are summarized in Table 14 below.

[0138] Table 14: Characterization properties of fluorinated copolymer 2:

[0139]

[0140]

[0141] Using the fluorinated copolymer 5, coatings were prepared according to the formulations described in Table 15:

[0142] Table 15: Coating Formulations (Contents in the table are in parts by weight)

[0143] Fluorinated copolymer 5 50 copies PMA 10 copies BAC 3.3 copies 6900-20X 0.6 copies Defoamer 0.1 copies DBE 2 copies NBA 2 copies 303 7 copies Titanium dioxide 25 copies

[0144] Example 6

[0145] In this embodiment, the fluorinated copolymer of this application was synthesized according to the following steps:

[0146] Add the components shown in Table 16 below to a 5000ml stainless steel autoclave equipped with a stirrer:

[0147] Table 16: Polymerization reaction raw materials used in Example 6

[0148]

[0149] 400g of n-butyl vinyl ether and 216g of hydroxybutyl vinyl ether were mixed to form a monomer mixture. Solvent, 80g of trifluorochloroethylene, and a stabilizer were added to the reactor. The temperature inside the reactor was raised to 54°C, and the initiator was added all at once to begin the polymerization reaction. The temperature inside the reactor was maintained at 54°C, and the monomer mixture and the remaining 760g of trifluorochloroethylene were continuously added over a 4-hour period. After the monomers were completely added, the reaction continued. The polymerization reaction was terminated after a total reaction time of 8 hours to obtain the FEVE resin semi-finished product.

[0150] The semi-finished product is transferred to a processing vessel, heated and concentrated to a solid content of 50 wt%. The material is then filtered to remove impurities, yielding a colorless and transparent product, denoted as fluorinated copolymer 6.

[0151] The test results for the fluorinated copolymer 6 are summarized in Table 17 below.

[0152] Table 17: Characterization properties of fluorinated copolymer 6:

[0153] Finished product solid content (50wt%) 50.82 Appearance Colorless and transparent Viscosity (mPa·s) 879 Acid value (mgKOH / g-polymer) 1.08 Hydroxyl value (mgKOH / g-polymer) 52.27 Fluorine content (F wt%) 26.10 Mn(g / mol) 15151 D 2.02 Inflection point Tg (°C) 10.32 Elongation at break % 171

[0154] Using the fluorinated copolymer 6, coatings were prepared according to the formulations described in Table 18:

[0155] Table 18: Coating Formulations (Contents in the table are in parts by weight)

[0156] Fluorinated copolymer 6 59.1 CAB381-0.5 (25%) 15 PMA 5 6900-20X 0.6 Deqian 432 0.2 Defoamer 0.1 DBE 2 NBA 2 303 8 Aluminum paste 8

[0157] Comparative Example 1

[0158] In this embodiment, a fluorinated copolymer was synthesized as a comparison according to the following steps:

[0159] Add the components shown in Table 19 below to a 5000ml stainless steel autoclave equipped with a stirrer:

[0160] Table 19: Polymerization reaction raw materials used in Comparative Example 1

[0161]

[0162]

[0163] 215g of ethyl vinyl ether, 216g of hydroxybutyl vinyl ether, and 114g of vinyl butyrate were mixed to form a monomer mixture. Solvent, 80g of trifluorochloroethylene, and a stabilizer were added to the reactor. The temperature inside the reactor was raised to 54°C, and the initiator was added all at once to begin the polymerization reaction. The temperature inside the reactor was maintained at 54°C, and the monomer mixture and the remaining 680g of trifluorochloroethylene were continuously added over a 4-hour period. After the monomers were completely added, the reaction continued. The polymerization reaction was terminated after a total reaction time of 8 hours to obtain the FEVE resin semi-finished product.

[0164] The semi-finished product is transferred to a processing vessel, heated and concentrated to a solid content of 50 wt%. The material is then filtered to remove impurities, yielding a colorless and transparent product, denoted as the comparative fluorinated copolymer.

[0165] The test results for the comparative fluorinated copolymers are summarized in Table 20 below.

[0166] Table 20: Comparison of the characterization properties of fluorinated copolymers:

[0167] Finished product solid content (50wt%) 50.29 Appearance Colorless and transparent Viscosity (mPa·s) 1003 Acid value (mgKOH / g-polymer) 0.89 Hydroxyl value (mgKOH / g-polymer) 59.41 Fluorine content (F wt%) 26.60 Mn(g / mol) 18376 D 2.1 Inflection point Tg (°C) 30.30 Elongation at break % 75

[0168] Using the comparative fluorinated copolymer, coatings were prepared according to the formulations described in Table 21:

[0169] Table 21: Coating Formulations (Contents in the table are in parts by weight)

[0170]

[0171]

[0172] Example 7: Weather Resistance Test

[0173] In this embodiment, the coatings formulated with the fluorinated copolymers obtained in Examples 1-6 and Comparative Example 1 were subjected to weather resistance tests.

[0174] Specifically, the coating sample was applied to an aluminum substrate with a thickness of 7-8 μm. The coated substrate was then placed in an infrared oven to dry overnight. The coated substrate was then placed in an ultraviolet light chamber and continuously irradiated with ultraviolet light emitting a peak wavelength of 313 nm. The gloss of the coating on the substrate surface was tested every 500 hours using a colorimeter / aging instrument. This experiment was conducted for 5000 hours.

[0175] The changes in gloss of the coatings prepared in Example 1 and Comparative Example 1 are as follows: Figure 1 As shown. The gloss retention rate (in percentage) of all Examples 1-6 and Comparative Example 1 after 5000 hours of UV aging was calculated according to the following formula.

[0176]

[0177] The test results are summarized in Table 22 below.

[0178] Table 22: 5000-hour UV aging results of Examples 1-6 and Comparative Example 1

[0179]

Claims

1. A fluorinated copolymer comprising copolymer units derived from monomers: The first monomer is tetrafluoroethylene; and the content of the first monomer is 52-54 mol% based on 100 mol% of the total molar amount of all monomers used to form the fluorinated copolymer. The second monomer is hydroxybutyl vinyl ether; and the content of the second monomer is 12-18 mol% based on 100 mol% of the total molar amount of all monomers used to form the fluorinated copolymer. The third monomer is ethyl vinyl ether and decyl vinyl ether; and the content of the third monomer is 28-35 mol% based on the total molar amount of all monomers used to form the fluorinated copolymer as 100 mol%; and the molar ratio of ethyl vinyl ether to decyl vinyl ether is 3:

1. The fluorinated copolymer does not contain copolymer units derived from vinyl esters.

2. The fluorinated copolymer as described in claim 1, characterized in that, The number-average molecular weight Mn of the fluorinated copolymer is from 5,000 to 50,000.

3. A coating / adhesive composition, comprising, based on 100% by weight of the total weight of the composition: 50-65% by weight of the fluorinated copolymer according to any one of claims 1-2; 0-50% by weight of one or more optional additives; and The remaining amount of solvent.

4. A roll material comprising a fluorinated copolymer as described in any one of claims 1-2, or comprising a coating / adhesive composition as described in claim 3.

5. A method for preparing the fluorinated copolymer according to any one of claims 1-2, the method comprising copolymerizing the first monomer, the second monomer, and the third monomer in the presence of an initiator and a solvent to form the fluorinated copolymer.

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