Weather-resistant fluorocarbon resin as well as preparation method and application thereof

Abstract

The invention provides weather-resistant fluorocarbon resin as well as a preparation method and application thereof. The resin comprises a copolymerization unit formed by the following monomers: a first perfluoroolefin monomer, a second alkyl vinyl ether monomer, a third hydroxyalkyl vinyl ether monomer and a fourth alkoxy vinyl ether monomer, the weight ratio of the copolymerized units formed from the first monomer to the copolymerized units formed from the second monomer is from 100: 5 to 100: 80; the weight ratio of the copolymerized units formed from the first monomer to the copolymerized units formed from the third monomer is 100: 10 to 100: 85; the weight ratio of the copolymerized units formed by the first monomer to the copolymerized units formed by the fourth monomer is 100: 15 to 100: 90. According to the invention, the fluorocarbon resin with a highly alternating structure and extremely excellent weather resistance is successfully prepared, and the fluorocarbon resin can be synthesized by a simple and low-cost process.

Description

Technical Field

[0001] The present application relates to the field of polymers, and more specifically to a fluorocarbon resin containing multiple comonomers, a preparation method of the fluorocarbon resin, and applications of the fluorocarbon resin in weather-resistant coatings and products. Background Art

[0002] Fluorocarbon resin refers to a polymer material containing fluorine atoms on the carbon atoms of the main chain or side chain, including fluoroolefin polymers such as polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polyperfluoroethylene propylene (FEP) or tetrafluoroethylene-ethylene copolymer (ETFE), etc., and may also include copolymers of fluoroolefins and other monomers such as chlorotrifluoroethylene (CTFE)-vinyl ether copolymers, tetrafluoroethylene (TFE)-vinyl ester copolymers, etc. Among them, FEVE fluorocarbon resin is a copolymer of fluorinated olefins and alkyl vinyl ether (ester). Compared with traditional fluorocarbon resins, FEVE fluorocarbon resins not only have excellent weather resistance, chemical resistance and corrosion resistance, but also have good solubility, do not require high-temperature baking to form a film, can be cured at room temperature to form a film, and have high gloss.

[0003] However, the performance of the FEVE fluorocarbon resins reported so far and their synthesis methods have always had some problems that need to be solved. For example, the fluoroolefin monomers in the existing FEVE fluorocarbon resins often have poor compatibility with other comonomers, resulting in local self-polymerization of a certain type of comonomer in the system during the polymerization reaction, rather than the alternating polymerization of multiple comonomers that people hope to see, which will lead to insufficient regularity of the alternating structure of the copolymerized fluorocarbon main chain, thereby significantly deteriorating its weather resistance and other properties. Therefore, people are in urgent need of improving the compatibility of various comonomers during the copolymerization process, significantly improving the regular arrangement of the molecular structure of FEVE fluorocarbon resins, and improving the alternation between fluorine-containing monomers and hydrocarbon monomers, thereby improving its weather resistance.

[0004] In order to solve the above problems, the inventors of the present application invested a lot of scientific research costs and energy in long-term and in-depth research, and successfully developed a new fluorocarbon resin and a synthesis method thereof. The various copolymer units in the polymer main chain of the fluorocarbon resin prepared in this way are in a highly alternating form, thereby exhibiting excellent weather resistance and other excellent properties, solving the long-standing problem that needs to be solved in the prior art. Summary of the invention

[0005] The first aspect of the present application provides a weather-resistant fluorocarbon resin, which comprises copolymer units formed by the following monomers:

[0006] (A) first monomer: C3-C8 perfluoroolefin;

[0007] (B) a second monomer having a structure shown in Formula I:

[0008]

[0009] Where R A represents a C1-C16 alkyl group or a C3-C12 cycloalkyl group, and R1, R2 and R3 are each independently hydrogen, halogen, C1-C6 alkyl group, C1-C6 alkoxy group or C3-C12 cycloalkyl group;

[0010] (C) a third monomer having a structure shown in Formula II,

[0011]

[0012] Where R B represents a C1-C16 hydroxyalkyl group containing at least one hydroxyl group or a C3-C12 hydroxycycloalkyl group containing at least one hydroxyl group; R4 represents a covalent bond or a C1-C6 alkylene group; R5, R6 and R7 are each independently hydrogen, halogen, C1-C6 alkyl, C1-C6 alkoxy or C3-C12 cycloalkyl;

[0013] (D) a fourth monomer having a structure shown in Formula III,

[0014]

[0015] Among them, R8, R9 and R 10 Each is independently hydrogen, halogen, C1-C6 alkyl, C1-C6 alkoxy or C3-C12 cycloalkyl; R 11 represents C1-C12 alkylene, n represents 1-10; R 12 It represents a C1-C12 alkyl group or a C3-C12 cycloalkyl group.

[0016] According to one embodiment of the present application, a weight ratio of the copolymerization unit formed of the first monomer to the copolymerization unit formed of the second monomer is 100:5 to 100:80.

[0017] According to another embodiment of the present application, a weight ratio of the copolymerization unit formed of the first monomer to the copolymerization unit formed of the third monomer is 100:10 to 100:85.

[0018] According to another embodiment of the present application, a weight ratio of the copolymerization unit formed of the first monomer to the copolymerization unit formed of the fourth monomer is 100:15 to 100:90.

[0019] According to another embodiment of the present application, the first monomer is selected from one or more of the following: hexafluoropropylene, octafluorobutene, hexafluoro-1,3-butadiene, decafluoropentene, octafluoro-isoprene, dodecafluorohexene, decafluoro-hexadiene.

[0020] According to another embodiment of the present application, the second monomer is selected from one or more of the following: ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, pentyl vinyl ether, hexyl vinyl ether, heptyl vinyl ether, octyl vinyl ether, dodecyl vinyl ether, hexadecyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, cyclopentyl vinyl ether, cyclobutyl vinyl ether, and cyclopropyl vinyl ether.

[0021] According to another embodiment of the present application, the third monomer is selected from one or more of the following: hydroxybutyl vinyl ether, hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, ethylene glycol monoallyl ether, hydroxypentyl vinyl ether, hydroxyhexyl vinyl ether, and hydroxycyclohexyl vinyl ether.

[0022] According to another embodiment of the present application, the fourth monomer is one or more compounds having a structure of formula III, wherein R8, R9 and R 10 are each independently hydrogen, methyl, ethyl or propyl; R 11 represents C1-C4 alkylene, n represents 1-3; R 12 It represents a C1-C4 alkyl group.

[0023] According to another embodiment of the present application, the weather-resistant fluorocarbon resin has a number average molecular weight of 5,000-80,000, a weight average molecular weight of 10,000-160,000, and a polydispersity (PDI) of 1.5-5.

[0024] The second aspect of the present application provides a method for preparing the weather-resistant fluorocarbon resin of the present application, the method comprising polymerizing a first monomer, a second monomer, a third monomer and a fourth monomer in a polymerization reactor to generate the weather-resistant fluorocarbon resin.

[0025] According to an embodiment of the second aspect of the present application, the method further includes adding a solvent, an auxiliary agent and an initiator to the polymerization reaction kettle. Based on the total weight of the solvent, auxiliary agent, initiator and all monomers added to the polymerization reaction kettle, the first monomer is 20-50% by weight, the second monomer is 3-15% by weight, the third monomer is 5-20% by weight, the fourth monomer is 5-20% by weight, the solvent is 30-60% by weight, the initiator is 0.1-2% by weight, and the auxiliary agent is 0.1-2% by weight.

[0026] According to another embodiment of the second aspect of the present application, the solvent is selected from one or more of the following: toluene, xylene, ethylbenzene, cyclohexane, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, amyl acetate, hexyl acetate, diethyl malonate, dibutyl malonate, acetone, methanol, chloroform, tetrahydrofuran, N,N-dimethylformamide, N-methylpyrrolidone. According to another embodiment of the second aspect of the present application, the auxiliary agent is selected from one or more of the following: sodium carbonate, ammonium carbonate, hindered amine 292, zinc oxide, magnesium oxide, sodium hydroxide, potassium hydroxide, triethylamine. According to another embodiment of the second aspect of the present application, the initiator is selected from one or more of the following: tert-butyl peroxypivalate, diisopropyl peroxydicarbonate, tert-amyl peroxypivalate, 3-hydroxy-1,1-dimethylbutyl peroxyneodecanoic acid, tert-butyl peroxyneodecanoic acid.

[0027] The third aspect of the present application provides a weather-resistant product, which comprises the weather-resistant fluorocarbon resin of the present application, and the weather-resistant product is a coating, a surface film or a cover sheet.

[0028] In the following specific implementation section, the fluorocarbon resin, preparation method and specific uses of the present application are further introduced in conjunction with the drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 The accelerated aging test results of the fluorocarbon resins prepared in various examples and comparative examples of the present application are shown. DETAILED DESCRIPTION

[0030] "Range" disclosed herein is in the form of lower limit and 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 limit and upper limit define the boundaries of a particular range. All ranges that can be defined in this way are inclusive and combinable, i.e. any lower limit can be combined with any upper limit to form a range. For example, a range of 60-120 and 80-110 is listed for a particular parameter, and it is understood that a range of 60-110 and 80-120 is also expected. In addition, if the minimum range values ​​1 and 2 are listed, and if the maximum range values ​​3, 4 and 5 are listed, the following ranges can all be expected: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5.

[0031] In this application, unless otherwise specified, the numerical range "ab" represents an abbreviation of any real number combination between a and b, where a and b are real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" are listed in this document, and "0-5" is just an abbreviation of these numerical combinations.

[0032] In this application, unless otherwise specified, all embodiments and preferred embodiments mentioned herein can be combined with each other to form a new technical solution.

[0033] In this application, unless otherwise specified, all technical features and preferred features mentioned herein can be combined with each other to form a new technical solution.

[0034] In this application, if there is no special explanation, the "including" mentioned herein means open or closed. For example, the "including" may mean that other components not listed may also be included, or only the listed components may be included.

[0035] In the present application, four specially designed different comonomers are used to undergo copolymerization reaction (more specifically, addition polymerization reaction of carbon-carbon double bonds) in a polymerization reactor to prepare the fluorocarbon resin described in the present application. In the present application, for the convenience of expression, the copolymerization unit formed by the polymerization reaction of the first monomer (specifically, the addition polymerization reaction of the carbon-carbon double bond in the first monomer) in the fluorocarbon resin product is referred to as the first copolymerization unit, the copolymerization unit formed by the polymerization reaction of the second monomer (specifically, the addition polymerization reaction of the carbon-carbon double bond of the vinyl in the second monomer) in the fluorocarbon resin product is referred to as the second copolymerization unit, the copolymerization unit formed by the polymerization reaction of the third monomer (specifically, the addition polymerization reaction of the carbon-carbon double bond of the vinyl in the third monomer) in the fluorocarbon resin product is referred to as the third copolymerization unit, and the copolymerization unit formed by the polymerization reaction of the fourth monomer (specifically, the addition polymerization reaction of the carbon-carbon double bond of the vinyl in the fourth monomer) in the fluorocarbon resin product is referred to as the fourth copolymerization unit. According to one embodiment of the present application, the main chain of the fluorocarbon resin is formed by addition polymerization of the carbon-carbon double bonds of the first, second, third and fourth monomers described above. One inventive point of the present application is that four different comonomers are selected so that the prepared fluorocarbon resin has a highly alternating structure and the desired excellent properties.

[0036] According to one embodiment of the present application, the first monomer used to prepare the fluorocarbon resin is a C3-C8 perfluoroolefin, such as a C3-C8 perfluoroolefin containing one, two or three carbon-carbon double bonds, such as a C3-C7 perfluoroolefin, or a C3-C6 perfluoroolefin, or a C3-C5 perfluoroolefin, or a C3-C4 perfluoroolefin, or a C3 perfluoroolefin. For example, the first monomer of the present application can be one or more of the following: hexafluoropropylene, octafluorobutene, hexafluoro-1,3-butadiene, decafluoropentene, octafluoro-isoprene, dodecafluorohexene, decafluoro-hexadiene. According to a particularly preferred embodiment of the present application, the first monomer is hexafluoropropylene. The second inventive point of the present application is that the inventors of the present application unexpectedly discovered through extensive research that these specially selected first monomers (especially hexafluoropropylene) are not easy to self-polymerize (for example, hexafluoropropylene is not easy to effectively form polyhexafluoropropylene homopolymer through self-polymerization) but can copolymerize well with some types of comonomers (the second monomer, the third monomer and the fourth monomer specially selected in the present application) and make the formed fluorocarbon resin product have a highly alternating structure and the desired excellent properties.

[0037] According to one embodiment of the present application, the second monomer is an alkyl vinyl ether having a structure shown in Formula I:

[0038]

[0039] Where R A represents C1-C16 alkyl or C3-C12 cycloalkyl, R1, R2 and R3 are each independently hydrogen, halogen, C1-C6 alkyl, C1-C6 alkoxy or C3-C12 cycloalkyl. For example, according to one embodiment, R AIt can be a C2-C12 alkyl or a C3-C10 cycloalkyl, such as a C3-C8 alkyl, or a C4-C6 alkyl, or a C3-C6 cycloalkyl. According to another specific embodiment, R1, R2 and R3 are each independently hydrogen, fluorine, chlorine, bromine, iodine, C1-C4 alkyl, C1-C4 alkoxy or C3-C12 cycloalkyl; or R1, R2 and R3 are each independently hydrogen, fluorine, chlorine, bromine, iodine, C1-C3 alkyl, C1-C3 alkoxy or C3-C8 cycloalkyl; or R1, R2 and R3 are each independently hydrogen, fluorine, chlorine, bromine, iodine, C1-C2 alkyl, C1-C2 alkoxy or C3-C6 cycloalkyl. According to an exemplary embodiment of the present application, the second monomer is selected from one or more of the following: ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, pentyl vinyl ether, hexyl vinyl ether, heptyl vinyl ether, octyl vinyl ether, dodecyl vinyl ether, hexadecyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, cyclopentyl vinyl ether, cyclobutyl vinyl ether, cyclopropyl vinyl ether. According to a particularly specific embodiment, the second monomer is butyl vinyl ether.

[0040] According to one embodiment of the present application, in the finally prepared fluorocarbon resin, the weight ratio of the first copolymerization unit to the second copolymerization unit is 100:5 to 100:80, for example, the weight ratio may be 100:8 to 100:75, or 100:10 to 100:70, or 100:15 to 100:65, or 100:16 to 100:60, or 100:18 to 100:55, or 100:19 to 100:50, or 100:20 to 100:45, or 100:22 to 100:40, or 100:25 to 100:35, or 100:26 to 100:30, or within the numerical range obtained by combining any two of the above end values.

[0041] A further inventive point of the present application is to select the type and relative content of the second monomer to obtain a fluorocarbon resin with a desired alternating structure and desired excellent properties.

[0042] According to one embodiment of the present application, the third monomer is a hydroxyalkyl vinyl ether having a structure shown in Formula II:

[0043]

[0044] Where R Brepresents a C1-C16 hydroxyalkyl group containing at least one hydroxyl group or a C3-C12 hydroxycycloalkyl group containing at least one hydroxyl group; R4 represents a covalent bond or a C1-C6 alkylene group; R5, R6 and R7 are each independently hydrogen, halogen, C1-C6 alkyl, C1-C6 alkoxy or C3-C12 cycloalkyl. For example, the R B It may represent a C1-C16 hydroxyalkyl group containing one, two or three hydroxy groups, or a C3-C12 hydroxycycloalkyl group containing one, two or three hydroxy groups, for example, a C1-C12 hydroxyalkyl group containing one or two hydroxy groups, or a C2-C8 hydroxyalkyl group containing one or two hydroxy groups, or a C3-C6 hydroxyalkyl group containing one or two hydroxy groups, or a C4-C5 hydroxyalkyl group containing one or two hydroxy groups, or a C3-C10 hydroxycycloalkyl group containing one or two hydroxy groups, or a C3-C8 hydroxycycloalkyl group containing one or two hydroxy groups, or a C3-C6 hydroxycycloalkyl group containing one or two hydroxy groups. According to another specific embodiment, R5, R6 and R7 are each independently hydrogen, fluorine, chlorine, bromine, iodine, C1-C4 alkyl, C1-C4 alkoxy or C3-C10 cycloalkyl; or R5, R6 and R7 are each independently hydrogen, fluorine, chlorine, bromine, iodine, C1-C3 alkyl, C1-C3 alkoxy or C3-C8 cycloalkyl; or R5, R6 and R7 are each independently hydrogen, fluorine, chlorine, bromine, iodine, C1-C2 alkyl, C1-C2 alkoxy or C3-C6 cycloalkyl.

[0045] According to an exemplary embodiment, the third monomer is selected from one or more of the following: hydroxybutyl vinyl ether, hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, ethylene glycol monoallyl ether, hydroxypentyl vinyl ether, hydroxyhexyl vinyl ether, hydroxycyclohexyl vinyl ether. According to a particularly specific embodiment, the third monomer is hydroxybutyl vinyl ether.

[0046] According to one embodiment of the present application, in the fluorocarbon resin finally prepared, the weight ratio of the first copolymerization unit to the third copolymerization unit is 100:10 to 100:85, for example, the weight ratio may be 100:12 to 100:80, or 100:14 to 100:75, or 100:15 to 100:70, or 100:16 to 100:65, or 100:17 to 100:60, or 100:18 to 100:55, or 100:19 to 100:50, or 100:20 to 100:45, or 100:21 to 100:40, or 100:22 to 100:35, or 100:25 to 100:30, or within the numerical range obtained by combining any two of the above end values.

[0047] A further inventive point of the present application is to design the type and relative content of the third monomer to obtain a fluorocarbon resin with a desired alternating structure and desired excellent properties.

[0048] According to one embodiment of the present application, the fourth monomer is an alkoxy vinyl ether having a structure shown in Formula III:

[0049]

[0050] Among them, R8, R9 and R 10 Each is independently hydrogen, halogen, C1-C6 alkyl, C1-C6 alkoxy or C3-C12 cycloalkyl; R 11 represents C1-C12 alkylene, n represents 1-10; R 12 It represents a C1-C12 alkyl group or a C3-C12 cycloalkyl group.

[0051] According to one embodiment of the present application, n represents 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10. R8, R9 and R 10 are each independently hydrogen, fluorine, chlorine, bromine, iodine, C1-C4 alkyl, C1-C4 alkoxy or C3-C10 cycloalkyl; or R8, R9 and R 10 are each independently hydrogen, fluorine, chlorine, bromine, iodine, C1-C3 alkyl, C1-C3 alkoxy or C3-C8 cycloalkyl; or R8, R9 and R 10 R is independently hydrogen, fluorine, chlorine, bromine, iodine, C1-C2 alkyl, C1-C2 alkoxy or C3-C6 cycloalkyl. 11 represents C1-C12 alkylene, or C2-C10 alkylene, or C2-C8 alkylene, or C2-C6 alkylene, or C2-C4 alkylene, or C2-C3 alkylene. 12 represents a C1-C12 alkyl group, or a C2-C10 alkyl group, or a C2-C8 alkyl group, or a C2-C6 alkyl group, or a C2-C4 alkyl group, or a C2-C3 alkyl group, or a C3-C12 cycloalkyl group, or a C3-C10 cycloalkyl group, or a C3-C8 cycloalkyl group, or a C3-C6 cycloalkyl group, or a C5-C6 cycloalkyl group. According to a specific embodiment of the present application, in the alkoxy vinyl ether represented by formula III, R8, R9 and R 10 is hydrogen, R 11 is ethylene, R 12 is ethyl, and n is 1, 2 or 3.

[0052] According to one embodiment of the present application, in the fluorocarbon resin finally prepared, the weight ratio of the first copolymerization unit to the fourth copolymerization unit is 100:15 to 100:90, for example, the weight ratio may be 100:16 to 100:85, or 100:17 to 100:80, or 100:18 to 100:75, or 100:19 to 100:70, or 100:20 to 100:65, or 100:21 to 100:60, or 100:22 to 100:55, or 100:23 to 100:50, or 100:24 to 100:45, or 100:25 to 100:40, or 100:26 to 100:35, or within the numerical range obtained by combining any two of the above end values.

[0053] A further inventive point of the present application is to design the type and relative content of the fourth monomer to obtain a fluorocarbon resin with a desired alternating structure and desired excellent properties.

[0054] According to a more specific embodiment of the present application, the weight ratio of the amount of the first monomer to the sum of the amounts of the other three monomers (the first monomer added to the reactor: (the second monomer + the third monomer + the fourth monomer)) is 100:30 to 100:300, or 100:50 to 100:200, or 100:90 to 100:110, or about 100:100.

[0055] According to one embodiment of the present application, the number average molecular weight of the fluorocarbon resin is 5000-80000, for example, 6000-75000, or 7000-70000, or 8000-60000, or 9000-50000, or 10000-40000, or 11000-30000, or 11000-20000, or 11000-150000, or within the numerical range obtained by combining any two of the above end values.

[0056] According to one embodiment of the present application, the weight average molecular weight of the fluorocarbon resin is 10000-160000, for example, 9000-150000, or 10000-140000, or 11000-120000, or 12000-100000, or 13000-90000, or 14000-80000, or 15000-70000, or 16000-60000, or 17000-50000, or 18000-40000, or 19000-35000, or 20000-320000, or 22000-320000, or 25000-30000, or within the numerical range obtained by combining any two of the above end values.

[0057] According to one embodiment of the present application, the polydispersity (PDI, Mw / Mn) of the fluorocarbon resin is 1.5-5, for example, 1.6-4.5, or 1.8-4.0, or 2.0-3.0, or 2.1-2.5, or 2.0-2.2, or 2.3-2.6, or within the numerical range obtained by combining any two of the above end values.

[0058] The fluorocarbon resin of the present application can be prepared by the following method: a first monomer, a second monomer, a third monomer and a fourth monomer are polymerized in a polymerization reactor to generate the weather-resistant fluorocarbon resin.

[0059] In the present application, the weather-resistant fluorocarbon resin has "high alternation" or "high alternation structure", that is, in the main chain of the fluorocarbon polymer, the polymer units connected to any polymer unit are very likely to be different polymer units, for example, a hexafluoropropylene polymer unit may be adjacent to an alkyl vinyl ether polymer unit, a hydroxyalkyl vinyl ether polymer unit or an alkoxy vinyl ether polymer unit, but is unlikely to be a hexafluoropropylene polymer unit. In the present invention, the irregular structure ratio in the fluorocarbon resin can be detected by nuclear magnetic resonance, and the lower the irregular structure ratio, the higher the degree of alternation of the structure of the fluorocarbon resin.

[0060] According to one embodiment of the present application, the fluorocarbon resin of the present application has a highly alternating structure, which is specifically manifested as: the proportion of irregular structures detected by nuclear magnetic resonance is less than 15%, for example, less than 12%, or less than 10%, or less than 8%, or less than 5%, or less than 2%, or less than 1%, for example, it can be 0.01-0.9%, or 0.1-0.9%, or 0.5-0.9%.

[0061] According to one embodiment of the present application, the method includes adding a solvent, an auxiliary agent and an initiator to a polymerization reactor. Based on the total weight of the solvent, auxiliary agent, initiator and all monomers added to the polymerization reactor, the first monomer is 20-50% by weight, for example, 25-45% by weight, or 30-40% by weight, or 35-48% by weight, or within the numerical range obtained by combining any two of the above end values; the second monomer is 3-15% by weight, for example, 4-12% by weight, or 5-10% by weight, or 6-8% by weight, or within the numerical range obtained by combining any two of the above end values; the third monomer is 5-20% by weight, for example, 6-18% by weight, or 8-16% by weight, or 10-15% by weight, or 12-14% by weight, or within the numerical range obtained by combining any two of the above end values; the fourth monomer is 5-20% by weight, for example, 6-18% by weight, or 8-16% by weight, or 10-15% by weight , or 12-14 wt %, or within the numerical range obtained by combining any two of the above end values; the solvent is 30-60 wt %, for example 35-55 wt %, or 38-52 wt %, or 40-50 wt %, or 42-48 wt %, or 45-46 wt %, or within the numerical range obtained by combining any two of the above end values; the initiator is 0.1-2 wt %, for example 0.2-1.8 wt %, or 0.4-1.6 wt %, or 0.5-1.5 wt %, or 0.6-1.2 wt %, or 0.8-1.0 wt %, or within the numerical range obtained by combining any two of the above end values; the auxiliary agent is 0.1-2 wt %, for example 0.20.2-1.8 wt %, or 0.4-1.6 wt %, or 0.5-1.5 wt %, or 0.6-1.2 wt %, or 0.8-1.0 wt %, or within the numerical range obtained by combining any two of the above end values.

[0062] According to one embodiment of the present application, the solvent is an organic solvent, for example, it can be selected from one or more of the following: toluene, xylene, ethylbenzene, cyclohexane, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, amyl acetate, hexyl acetate, diethyl malonate, dibutyl malonate, acetone, methanol, chloroform, tetrahydrofuran, N,N-dimethylformamide, N-methylpyrrolidone.

[0063] According to one embodiment of the present application, the auxiliary agent may be a carbonate, an organic amine, a metal oxide, an alkali metal hydroxide, for example, one or more selected from the following: sodium carbonate, ammonium carbonate, hindered amine 292, zinc oxide, magnesium oxide, sodium hydroxide, potassium hydroxide, triethylamine;

[0064] According to one embodiment of the present application, the initiator is an organic peroxide, for example, it can be selected from one or more of the following: tert-butyl peroxypivalate, diisopropyl peroxydicarbonate, tert-amyl peroxypivalate, 3-hydroxy-1,1-dimethylbutyl peroxyneodecanoic acid, tert-butyl peroxyneodecanoate.

[0065] According to a specific embodiment of the present application, the method of the present invention can be carried out in the following manner: first add the solvent and the auxiliary agent into the reactor, evacuate the reactor to replace the gas therein, until the oxygen content is <20ppm. At this time, start the stirring device of the reactor, heat it to the first reaction temperature, add a certain amount of initiator into the reactor, and at the same time, according to the designed copolymerization ratio, respectively add the first monomer, the second monomer, the third monomer and the fourth monomer into the reactor within a period of time. After the monomer raw material is added dropwise, add a certain amount of initiator into the reactor, heat it to the second reaction temperature, and continue to react for a period of time. After the reaction is completed, cool down, discharge, for example, filter, and then reduce the pressure and concentrate the filtered solution to a predetermined solid content, remove excess solvent and residual monomers to obtain the above-mentioned fluorocarbon resin.

[0066] According to a specific embodiment of the present application, the first monomer is added to the reactor in gas phase, and the second monomer, the third monomer and the fourth monomer are all added to the reactor in liquid phase.

[0067] According to one embodiment of the present application, the temperature of the above polymerization reaction can be 40-100° C., such as 45-90° C., or 50-60° C., or 70-90° C. According to a specific embodiment of the present application, the first reaction temperature mentioned above can be 45-60° C., such as 50-55° C.; the second reaction temperature mentioned above can be 60-100° C., such as 70-90° C.

[0068] The fluorocarbon resin of the present application can be used in various products that require weather protection, such as coatings, surface films or cover sheets, for example, in buildings, bridges, steel structures, vehicles, furniture, roofs, doors and windows, furniture, industrial equipment, aviation, aerospace, ships, etc.

[0069] The present application is described below in the form of specific examples, and its purpose is to better understand the content of the present application. It should be understood that these examples are merely illustrative and non-restrictive. The reagents used in the examples are conventionally purchased from the market unless otherwise specified. The methods and conditions used in the examples are conventional methods and conditions unless otherwise specified.

[0070] Example

[0071] In the following examples, the raw materials used are all commercially available analytically pure samples, which are used directly without further purification or treatment. The ethoxylated vinyl ether used in the following examples is (C2H5-O)-(C2H4-O)-CH=CH2. The "parts" mentioned in the following examples are all "parts by weight".

[0072] In the following examples, the fluorocarbon resin is characterized by the following techniques: the solid content of the fluorocarbon resin is measured by the oven weight loss method; the viscosity of the fluorocarbon resin product is tested at 25°C using a rotary viscometer; the fluorocarbon resin is burned by the combustion method and then titrated with a standard reagent to determine the fluorine content of the fluorocarbon resin; the acid value of the fluorocarbon resin is titrated with bromothymol blue indicator; the hydroxyl value of the acetic anhydride fluorocarbon resin is titrated with phenolphthalein indicator; the fluorocarbon resin is dissolved in THF solvent and the molecular weight and distribution of the fluorocarbon resin are measured by APC; the weather resistance of the fluorocarbon resin after being made into a coating is determined by an ultraviolet accelerated aging instrument; based on 19 F-NMR spectrum, calculation of irregular structure of fluorocarbon resin: In the NMR fluorine spectrum of fluorocarbon resin prepared in the following examples and comparative examples, the peak at the chemical shift of -211.84ppm is attributed to the fluorine atom on -CF- in the structure of HFP-HFP directly connected, which is an irregular structure; the peak at the chemical shift of -182.69ppm is attributed to the fluorine atom on -CF- in the HFP-CH2-CH(R)-HFP structure of indirect connection with vinyl ester (ether) monomer in the middle, which is an alternating regular structure. Therefore, the calculation method of irregular structure is as follows:

[0073] Irregular structure ratio = S (-211.84ppm) / S (-211.84ppm) +S (-182.69ppm) *100%

[0074] Where S (某ppm) Represents the NMR integrated peak area at the chemical shift indicated in brackets.

[0075] When conducting the UV accelerated aging test, the fluorocarbon resin is prepared into a coating through the following steps, and then subjected to the UV accelerated aging test: 55 parts of fluorocarbon resin are weighed, added to 8 parts of PMA and 3.7 parts of BAC solvent, and then added to 0.5 parts of dispersant and 0.5 parts of defoamer, placed on the dispersant and stirred to disperse and mix evenly; 0.5 parts of thixotropic agent, 10 parts of pigment, 20 parts of titanium dioxide, and 0.3 parts of leveling agent are added under stirring, and after dispersing for 15 minutes, glass beads are added for sand grinding to a fineness of less than 20 microns. 1.5 parts of curing agent are added before spraying the plate, and the above coating is sprayed on the plate to make a coating.

[0076] Example 1

[0077] 49 parts of xylene and 0.5 parts of sodium carbonate were added to the reactor, and the reactor was evacuated to replace the air therein until the oxygen content was qualified <20ppm. The stirring device was turned on, the temperature of the reactor was raised to 55°C, 0.5 parts of tert-butyl peroxy pivalate were added to the reactor, and 27 parts of hexafluoropropylene, 8 parts of hydroxybutyl vinyl ether, 5 parts of butyl vinyl ether, and 10 parts of ethoxy vinyl ether were added dropwise to the reactor within 3 hours to carry out solution polymerization. After the addition was completed, 0.1 parts of tert-butyl peroxy pivalate were added, and the temperature of the reactor was raised to 80°C, and the reaction was continued for 2 hours. After the reaction was completed, the temperature of the reactor was lowered to room temperature, the materials in the reactor were discharged, and the solvent and residual monomers were concentrated to obtain a fluorocarbon resin product.

[0078] The properties of the fluorocarbon resin were characterized according to the above-mentioned techniques. The test results of the fluorocarbon resin are shown in Table 1. The weather resistance test results are shown in Figure 1 shown.

[0079] Example 2

[0080] 39 parts of xylene and 0.5 parts of sodium carbonate were added to the reactor, and the reactor was evacuated to replace the air therein until the oxygen content was qualified <20ppm. The stirring device was turned on, the temperature of the reactor was raised to 55°C, 0.5 parts of tert-butyl peroxy pivalate were added to the reactor, and 38 parts of hexafluoropropylene, 7 parts of hydroxybutyl vinyl ether, 10 parts of butyl vinyl ether, and 10 parts of ethoxy vinyl ether were added dropwise to the reactor within 3 hours to carry out solution polymerization. After the addition was completed, 0.1 parts of tert-butyl peroxy pivalate were added, and the temperature of the reactor was raised to 80°C, and the reaction was continued for 2 hours. After the reaction was completed, the temperature of the reactor was lowered to room temperature, the materials in the reactor were discharged, and the solvent and residual monomers were concentrated to obtain a fluorocarbon resin product.

[0081] The properties of the fluorocarbon resin were characterized according to the above-mentioned techniques. The test results of the fluorocarbon resin are shown in Table 1. The weather resistance test results are shown in Figure 1 shown.

[0082] Comparative Example 1

[0083] 33 parts of xylene and 0.5 parts of sodium carbonate were added to the reactor, and the reactor was evacuated to replace the air therein until the oxygen content was qualified <20ppm. The stirring device was turned on, the temperature of the reactor was raised to 55°C, 0.5 parts of tert-butyl peroxy pivalate were added to the reactor, and 34 parts of chlorotrifluoroethylene, 7 parts of hydroxybutyl vinyl ether, 12 parts of butyl vinyl ether, and 13 parts of ethoxy vinyl ether were added dropwise to the reactor within 3 hours to carry out solution polymerization. After the addition was completed, 0.1 parts of tert-butyl peroxy pivalate were added, and the temperature of the reactor was raised to 80°C, and the reaction was continued for 2 hours. After the reaction was completed, the temperature of the reactor was lowered to room temperature, the materials in the reactor were discharged, and the solvent and residual monomers were concentrated to obtain a fluorocarbon resin product.

[0084] The properties of the fluorocarbon resin were characterized according to the above-mentioned techniques. The test results of the fluorocarbon resin are shown in Table 1. The weather resistance test results are shown in Figure 1 shown.

[0085] Comparative Example 2

[0086] 33 parts of xylene and 0.5 parts of sodium carbonate were added to the reactor, and the reactor was evacuated to replace the air therein until the oxygen content was qualified <20ppm. The stirring device was turned on, the temperature of the reactor was raised to 55°C, 0.5 parts of tert-butyl peroxy pivalate were added to the reactor, and 30 parts of tetrafluoroethylene, 7 parts of hydroxybutyl vinyl ether, 12 parts of butyl vinyl ether, and 13 parts of ethoxy vinyl ether were added dropwise to the reactor within 3 hours to carry out solution polymerization. After the addition was completed, 0.1 parts of tert-butyl peroxy pivalate were added, and the temperature of the reactor was raised to 80°C, and the reaction was continued for 2 hours. After the reaction was completed, the temperature of the reactor was lowered to room temperature, the materials in the reactor were discharged, and the solvent and residual monomers were concentrated to obtain a fluorocarbon resin product.

[0087] The properties of the fluorocarbon resin were characterized according to the above-mentioned techniques. The test results of the fluorocarbon resin are shown in Table 1. The weather resistance test results are shown in Figure 1 shown.

[0088] From Table 1 and Figure 1 It can be seen from the experimental results that the fluorocarbon resin prepared in the examples of the present application has an extremely high alternating structure and extremely excellent weather resistance.

[0089] Table 1 Test results of fluorocarbon resin

[0090]

Claims

1. A weather-resistant fluorocarbon resin comprising copolymer units formed by the following monomers: (A) first monomer: C3-C8 perfluoroolefin; (B) a second monomer having a structure shown in Formula I: Where R A represents a C1-C16 alkyl group or a C3-C12 cycloalkyl group, and R1, R2 and R3 are each independently hydrogen, halogen, C1-C6 alkyl group, C1-C6 alkoxy group or C3-C12 cycloalkyl group; (C) a third monomer having a structure shown in Formula II, Where R B represents a C1-C16 hydroxyalkyl group containing at least one hydroxyl group or a C3-C12 hydroxycycloalkyl group containing at least one hydroxyl group; R4 represents a covalent bond or a C1-C6 alkylene group; R5, R6 and R7 are each independently hydrogen, halogen, C1-C6 alkyl, C1-C6 alkoxy or C3-C12 cycloalkyl; (D) a fourth monomer having a structure shown in Formula III, Among them, R8, R9 and R 10 Each is independently hydrogen, halogen, C1-C6 alkyl, C1-C6 alkoxy or C3-C12 cycloalkyl; R 11 represents C1-C12 alkylene, n represents 1-10; R 12 represents a C1-C12 alkyl group or a C3-C12 cycloalkyl group; The weight ratio of copolymerized units formed from the first monomer to copolymerized units formed from the second monomer is 100:5 to 100:80; The weight ratio of the copolymerized units formed from the first monomer to the copolymerized units formed from the third monomer is 100:10 to 100:85; A weight ratio of the copolymerization units formed from the first monomer to the copolymerization units formed from the fourth monomer is 100:15 to 100:

90.

2. The weather-resistant fluorocarbon resin according to claim 1, characterized in that: The first monomer is selected from one or more of the following: hexafluoropropylene, octafluorobutene, hexafluoro-1,3-butadiene, decafluoropentene, octafluoro-isoprene, dodecafluorohexene, decafluoro-hexadiene.

3. The weather-resistant fluorocarbon resin according to claim 1, characterized in that: The second monomer is selected from one or more of the following: ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, pentyl vinyl ether, hexyl vinyl ether, heptyl vinyl ether, octyl vinyl ether, dodecyl vinyl ether, hexadecyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, cyclopentyl vinyl ether, cyclobutyl vinyl ether, and cyclopropyl vinyl ether.

4. The weather-resistant fluorocarbon resin according to claim 1, characterized in that: The third monomer is selected from one or more of the following: hydroxybutyl vinyl ether, hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, ethylene glycol monoallyl ether, hydroxypentyl vinyl ether, hydroxyhexyl vinyl ether, and hydroxycyclohexyl vinyl ether.

5. The weather-resistant fluorocarbon resin according to claim 1, characterized in that: The fourth monomer is one or more compounds having a structure of formula III, wherein R8, R9 and R 10 are each independently hydrogen, methyl, ethyl or propyl; R 11 represents C1-C4 alkylene, n represents 1-3; R 12 It represents a C1-C4 alkyl group.

6. The weather-resistant fluorocarbon resin according to claim 1, characterized in that: The weather-resistant fluorocarbon resin has a number average molecular weight of 5,000-80,000, a weight average molecular weight of 10,000-160,000, and a polydispersity (PDI) of 1.5-5.

7. A method for preparing the weather-resistant fluorocarbon resin according to any one of claims 1 to 6, the method comprising polymerizing a first monomer, a second monomer, a third monomer and a fourth monomer in a polymerization reactor to generate the weather-resistant fluorocarbon resin.

8. The method according to claim 7, characterized in that The method also includes adding a solvent, an auxiliary agent and an initiator into the polymerization reaction kettle. Based on the total weight of the solvent, auxiliary agent, initiator and all monomers added to the polymerization reaction kettle, the first monomer is 20-50% by weight, the second monomer is 3-15% by weight, the third monomer is 5-20% by weight, the fourth monomer is 5-20% by weight, the solvent is 30-60% by weight, the initiator is 0.1-2% by weight, and the auxiliary agent is 0.1-2%.

9. The method according to claim 7, characterized in that The solvent is selected from one or more of the following: toluene, xylene, ethylbenzene, cyclohexane, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, pentyl acetate, hexyl acetate, diethyl malonate, dibutyl malonate, acetone, methanol, chloroform, tetrahydrofuran, N,N-dimethylformamide, N-methylpyrrolidone; The auxiliary agent is selected from one or more of the following: sodium carbonate, ammonium carbonate, hindered amine 292, zinc oxide, magnesium oxide, sodium hydroxide, potassium hydroxide, triethylamine; The initiator is selected from one or more of the following: tert-butyl peroxypivalate, diisopropyl peroxydicarbonate, tert-amyl peroxypivalate, 3-hydroxy-1,1-dimethylbutyl peroxyneodecanoic acid, and tert-butyl peroxyneodecanoate.

10. A weather-resistant product comprising the weather-resistant fluorocarbon resin according to any one of claims 1 to 6, wherein the weather-resistant product is a coating, a surface film or a cover sheet.

Images