CN109534993B - Unsaturated fluorocarbon compound and preparation method and application thereof - Google Patents
Unsaturated fluorocarbon compound and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides an unsaturated fluorocarbon compound and a preparation method and application thereof. The material prepared from the unsaturated fluorocarbon has excellent dielectric property and mechanical property, and is simple in preparation process, low in raw material price, and capable of effectively reducing investment and cost.
Description
Technical Field
The invention belongs to the field of communication materials, and relates to an unsaturated fluorocarbon compound, and a preparation method and application thereof.
Background
The 5G network is a fifth generation communication network, and its performance is superior to the 4G network technology used today. The 5G network technology is obviously embodied in the aspects of transmission timeliness, coverage, communication safety guarantee and the like of wireless signals. The 5G network communication technology is deeply combined with other wireless mobile technologies to form a brand new communication network, and the requirement of the internet mobile communication network for increasing speed is met. Moreover, the 5G mobile network technology can also realize mutual adjustment between intellectualization and automation, and has certain flexibility, because the communication technology and wireless technology used by people nowadays lay a good foundation for the 5G communication system.
The main goal of 5G networks is to keep the end user always in a networked state. The future 5G networks will support far more than smart phones-it will also support smart watches, fitness wristbands, smart home devices such as bird's nest type indoor thermostats, etc. The 5G network refers to a next generation wireless network. A 5G network would be a real upgrade of a 4G network, whose basic requirements are different from today's wireless networks. The transmission rate of the future 5G network can reach 10Gbps, which means that a mobile phone user can complete the downloading of a high-definition movie in less than one second.
The communication material for 5G requires a material with very low dielectric constant and dielectric loss, and the materials used in the current 4G communication take polytetrafluoroethylene as the main material, the polytetrafluoroethylene is coated on a copper foil, and bonding is performed if the performance is rough by using laser or chemical method. However, the multi-layer capability of the polytetrafluoroethylene material is poor, the requirement of multi-layer of the 5G base station material cannot be met, and meanwhile, the polytetrafluoroethylene material is usually produced in a large area during preparation, so that the material with small size is difficult to manufacture, and the application to the 5G communication terminal is hindered. And the glass transition temperature of the polytetrafluoroethylene is low, and the stability of the polytetrafluoroethylene is also defective because a large amount of heat is generated by high-power communication transmission.
Disclosure of Invention
In order to solve the technical problems, the invention provides an unsaturated fluorocarbon compound, a preparation method and an application thereof, wherein the communication material has low dielectric constant and dielectric loss, excellent mechanical properties and heat resistance, and is suitable for communication base stations and terminals.
In order to achieve the purpose, the invention adopts the following technical scheme:
one of the objects of the present invention is to provide an unsaturated fluorocarbon compound prepared by intermolecular elimination reaction of a fluoroalcohol and a compound having at least one unsaturated group.
Preferably, the fluoroalcohol has a fluorine content of 25 to 67%, such as 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, or 67%, but not limited to the values addressed, and other values not listed in this range of values are equally applicable.
In the present invention, the fluoroalcohol is preferably perfluoroalcohol.
Preferably, the fluoroalcohol comprises a fluoroalcohol of C4-C18, such as any one of C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17 or C18, preferably a fluoroalcohol of C6-C12.
In the present invention, the fluoroalkyl alcohol is a linear or branched alkyl alcohol having 4 to 18 carbon atoms, wherein all or part of the hydrogen atoms in the alkyl chain are replaced by fluorine atoms, except for the hydrogen atom on the α carbon. Preferred in the present invention are perfluorinated linear alkyl alcohols having the formula F3C-(CF2)n-CH2And OH, wherein n is a positive integer of 2-16, and preferably n is 4-10.
In a preferred embodiment of the present invention, the compound having at least one unsaturated group is a compound having at least one hydroxyl group, mercapto group or carboxyl group.
In the present invention, the compound having at least one unsaturated group further has at least one reactive group, and the reactive group may be a hydroxyl group, a mercapto group, a carboxyl group, or the like, but is not limited to the above-mentioned groups, and may be any group that reacts with a hydroxyl group in perfluoroalcohol. For example, any one of 4-vinylbenzoic acid, 2-methyl-1, 4-dihydrobenzoic acid, 5-vinyl-2-pyridinecarboxylic acid, but not limited to, but is not limited to, butanol-3-ene, 3- (3-ene-butyl) phenol, hydroxydicyclopentadiene, octanol-7-ene, 6, 8-divinyl-2 naphthol, and 4- (5-ene-hexyl) -thiophenol.
As a preferable technical solution of the present invention, the intermolecular elimination reaction includes any one of an etherification reaction, a thioetherification reaction, or an esterification reaction.
In the present invention, the intermolecular elimination reaction is a reaction of removing a small molecule compound between compound a and compound B to obtain a-B compound, the small molecule may be water, hydrogen halide, hydrogen sulfide, methanol, or the like, and the corresponding reaction may be an etherification reaction, a thioetherification reaction, an esterification reaction, an amidation reaction, an ester exchange reaction, or the like.
In the present invention, the compounds described are typically, but not by way of limitation, of the formula:
any one of them.
The second objective of the present invention is to provide a preparation method of the unsaturated fluorocarbon compound, which comprises: the fluoroalcohol is prepared by intermolecular elimination reaction with a compound containing at least one unsaturated group.
The present invention also provides a fluorocarbon prepolymer prepared by polymerizing the unsaturated fluorocarbon compound of the present invention.
The fourth purpose of the invention is to provide an application of the unsaturated fluorocarbon or fluorocarbon prepolymer, wherein the unsaturated fluorocarbon or fluorocarbon prepolymer is used for preparing bonding sheets, copper-clad plates and circuit boards.
In a preferred embodiment of the present invention, the adhesive sheet is prepared from a resin composition.
Preferably, the resin composition comprises the unsaturated fluorocarbon compound and/or the fluorocarbon prepolymer and a hydrocarbon resin, or comprises a fluorocarbon polymer obtained by polymerization reaction of the unsaturated fluorocarbon compound and/or the fluorocarbon prepolymer and a hydrocarbon resin.
In the present invention, the polymerization reaction is preferably a radical polymerization, i.e., the unsaturated bond (such as a carbon-carbon double bond and a carbon-carbon triple bond) of the unsaturated fluorocarbon provided by the present invention is polymerized under the action of an initiator. The free radical polymerization can be the self-polymerization of the unsaturated fluorocarbon compound, and also can be the copolymerization of the unsaturated fluorocarbon compound and other additives containing unsaturated bonds.
In the invention, the fluorocarbon polymer prepared by polymerization reaction of the fluorocarbon compound or the fluorocarbon prepolymer is in a normal-temperature liquid state or a solid state soluble in a solvent. The fluorocarbon polymer is liquid or soluble solid at normal temperature, so that the fluorocarbon polymer is easy to process and is easy to be added and mixed with other additives, and the processing cost is reduced. Meanwhile, the material is easier to be used for manufacturing small-size devices, so that the material can be used for manufacturing small or miniature communication terminals such as mobile phones, notebook computers or tablet computers.
As the preferred technical scheme of the invention, the preparation method of the copper-clad plate comprises the following steps: the resin composition is dispersed in a solvent to prepare a resin glue solution, the resin glue solution is coated on the surface of a substrate to obtain a prepreg plate, metal foils are attached to one side or two sides of the prepreg plate to obtain a copper-clad plate, or at least two layers of prepreg plates are overlapped to obtain a plurality of layers of prepreg plates, and the metal foils are attached to one side or two sides of the plurality of layers of prepreg plates to obtain the copper-clad plate.
Preferably, the solvent is one or a combination of at least two of ketones, hydrocarbons, ethers, esters or aprotic solvents, preferably one or a mixture of at least two of acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, methanol, ethanol, primary alcohols, ethylene glycol monomethyl ether, propylene glycol methyl ether acetate, ethyl acetate, N-dimethylformamide or N, N-diethylformamide, and the combination is typically but not limited to: a combination of acetone and methyl ethyl ketone, a combination of methyl ethyl ketone and methyl isobutyl ketone, a combination of toluene and xylene, a combination of methanol and ethanol, a combination of ethanol and isopropanol, a combination of ethylene glycol monomethyl ether and propylene glycol monomethyl ether, a combination of propylene glycol methyl ether acetate and ethyl acetate, a combination of N, N-dimethylformamide and N, N-diethylformamide or a combination of methanol, ethylene glycol monomethyl ether and methyl ethyl ketone.
Preferably, the substrate is any one of a glass fiber substrate, a polyester substrate, a polyimide substrate, a ceramic substrate, or a carbon fiber substrate.
Preferably, the circuit board is formed by processing a circuit on the surface of the copper-clad plate.
The fluorocarbon polymer prepared by polymerization reaction of the fluorocarbon or fluorocarbon prepolymer provided by the invention has extremely low dielectric constant and dielectric loss, meets the requirements of 5G communication technology on the dielectric constant and dielectric loss of materials, and meanwhile, the communication material has good heat resistance and mechanical properties, and is more suitable for manufacturing high-power communication equipment.
According to the invention, the provided unsaturated fluorocarbon can be mixed and copolymerized with raw materials such as vinyl POSS (polyhedral oligomeric silsesquioxane), hydrocarbon resin and the like, or materials obtained by free radical polymerization of unsaturated fluorocarbon or fluorocarbon prepolymer can be mixed with raw materials such as vinyl POSS, hydrocarbon resin and the like, and the plate prepared by high-temperature molding of the two mixtures has excellent mechanical property and dielectric property, and is suitable for construction of a 5G communication base station.
Moreover, polytetrafluoroethylene has many difficulties in processing due to its melting point as high as 327 ℃, and has a critical surface tension of only 18 × 10-5N·cm-1The adhesive used in the preparation of the multilayer sheet has a tensile force greater than 18X 10-5N·cm-1And the uniform coating of the adhesive on the surface of the polytetrafluoroethylene is not facilitated, so that the polytetrafluoroethylene material has good dielectric properties, but is difficult to be used for preparing a multilayer board. Because the signal transmitting power of high-frequency high-speed communication, especially 5G communication, is much higher than that of the existing 4G communication technology, and because the volumes of the base station and the communication equipment are limited, a single-layer board is difficult to meet the requirements, and a multilayer circuit board is needed to increase the area of a circuit, thereby increasing the transmitting power. The fluorocarbon material provided by the invention has lower dielectric property than polytetrafluoroethylene material on the premise that the dielectric property is close to that of the polytetrafluoroethylene material and the requirement of high-frequency high-speed communication can be metMelting point and higher critical surface tension, and is suitable for the production of multilayer boards.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) the invention provides an unsaturated fluorocarbon compound, wherein a high molecular compound obtained by polymerizing the compound has excellent dielectric property and the dielectric constant can be as low as 2.2C2/N·M2The dielectric loss can be as low as 2.8 x 10-4The method is suitable for the high-frequency and high-speed communication fields such as 5G communication and the like;
(2) the invention provides an unsaturated fluorocarbon compound, and the plate prepared by mixing the compound with other additives has excellent mechanical property and dielectric property, the property is comprehensively superior to that of the traditional polytetrafluoroethylene plate, and the unsaturated fluorocarbon compound is more suitable for building a 5G communication base station;
(3) the invention provides an unsaturated fluorocarbon compound, which has lower melting point and higher critical surface tension than polytetrafluoroethylene on the premise that the dielectric property of the compound is close to that of the polytetrafluoroethylene material and the requirement of high-frequency high-speed communication can be met, and is suitable for production of multilayer plates.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The invention provides an unsaturated fluorocarbon compound, which has a structure shown in a formula I:
the preparation method of the compound shown in the formula I comprises the following steps: mixing 1mol of perfluorododecanol and 1.2mol of 4-vinyl-benzoic acid, adding 100mL of 0.1mol/L sodium hydroxide solution, mechanically stirring, heating at 80 ℃ for reaction for 2h, cooling to room temperature, washing with 500mL of water for 5 times, separating, adding anhydrous sodium sulfate, standing for 2h, and filtering to obtain the compound shown in the formula I.
1H NMR(CDCl3,500MHz):δ7.95～7.89(m，2H，Ar-H)，7.43～7.36(m，2H，Ar-H)，6.65～6.60(m，H，CH2＝CH)，5.63～5.57(t，H，CH 2＝CH)，5.21～5.16(t，H，CH 2＝CH)，4.62～4.55(s，2H，CH2)。
Example 2
The invention provides an unsaturated fluorocarbon compound, the structure of which is shown in formula II:
the preparation method of the compound shown in the formula II comprises the following steps: mixing 1mol of perfluorobutanol with 1.2mol of 2-methyl-1, 4-dihydrobenzoic acid, adding 100mL of 0.1mol/L sodium hydroxide solution, mechanically stirring, heating to react at 80 ℃ for 2.5h, cooling to room temperature, washing with 500mL of water for 5 times, separating liquid, adding anhydrous sodium sulfate, standing for 2h, and filtering to obtain the compound shown in the formula II.
1H NMR(CDCl3,500MHz):δ5.58～5.48(m，H，CH＝CH)，5.38～5.30(t，H，CH＝C)，4.45～4.39(s，2H，CH2)，3.71～3.65(d，H，CH)，2.67～2.60(t，2H，CH2)，1.75～1.68(t，3H，CH3)。
Example 3
The invention provides an unsaturated fluorocarbon compound, which has a structure shown in a formula III:
the preparation method of the compound shown in the formula III comprises the following steps: mixing 1mol of perfluorooctanol with 1.2mol of 5-vinyl-2-picolinic acid, adding 100mL of 0.1mol/L sodium hydroxide solution, mechanically stirring, heating to react at 70 ℃ for 3h, cooling to room temperature, washing with 500mL of water for 5 times, separating liquid, adding anhydrous sodium sulfate, standing for 2h, and filtering to obtain the compound shown in formula III.
1H NMR(CDCl3,500MHz):δ9.03～8.96(m，H，Ar-H)，8.23～8.15(m，2H，Ar-H)，6.66～6.61(m，H，CH2＝CH)，5.71～5.65(t，H，CH 2＝CH)，5.28～5.22(t，H，CH 2＝CH)，4.67～4.61(s，2H，CH2)。
Example 4
The invention provides an unsaturated fluorocarbon compound, the structure of which is shown as the formula X:
the preparation method of the compound shown in the formula IV comprises the following steps: mixing 1.2mol of perfluorooctanol with 1mol of methyl allyl alcohol, adding 20mL of concentrated sulfuric acid, mechanically stirring and heating until reflux reaction is carried out for 2.5h, cooling to room temperature, washing with 500mL of water for 5 times, separating liquid, adding anhydrous sodium sulfate, standing for 2h, and filtering to obtain the compound shown in formula IV.
1H NMR(CDCl3,500MHz):δ5.05～4.95(s，2H，CH2＝C)，4.08～4.01(s，2H，CH2)，3.72～3.65(s，2H，CH2)，1.75～1.68(s，3H，CH3)。
Example 5
The invention provides an unsaturated fluorocarbon compound, which has a structure shown in a formula V:
the preparation method of the compound shown in the formula V comprises the following steps: mixing 1.2mol of perfluorononanol and 1mol of phenol, adding 20mL of concentrated sulfuric acid, mechanically stirring and heating until reflux reaction is carried out for 2.5h, cooling to room temperature, washing for 5 times by 500mL of water, separating liquid, adding anhydrous sodium sulfate, standing for 2h, filtering, mixing the obtained solid with 1mol of 4-chloro-1-butene, adding 0.1mol of aluminum trichloride, reacting for 1.5h at 60 ℃, cooling to room temperature, washing for 5 times by 500mL of water, separating liquid, adding anhydrous sodium sulfate, standing for 2h, and filtering to obtain the compound shown in the formula V.
1H NMR(CDCl3,500MHz):δ7.32～7.27(m，H，Ar-H)，7.10～7.05(m，H，Ar-H)，6.88～6.78(m，2H，Ar-H)，5.85～5.79(m，H，CH2＝CH)，5.10～4.98(t，H，CH 2＝CH)，4.28～4.23(s，2H，CH2)，2.58～2.52(t，H，CH2)，2.31～2.26(m，2H，CH2)。
Example 6
The invention provides an unsaturated fluorocarbon compound, the structure of which is shown in formula VI:
the preparation method of the compound shown in the formula VI comprises the following steps: mixing 1.3mol of perfluorooctadecanol with 1mol of hydroxyl dicyclopentadiene, adding 20mL of concentrated sulfuric acid, mechanically stirring and heating until reflux reaction is carried out for 2h, cooling to room temperature, washing for 5 times with 500mL of ethanol, separating liquid, and carrying out reduced pressure distillation on residual ethanol to obtain the compound shown in the formula VI.
1H NMR(CDCl3,500MHz):δ5.84～5.78(m，H，CH2＝CH)，5.10～4.98(t，2H，CH 2＝CH)，3.72～3.66(t，2H，CH2)，3.41～3.35(t，2H，CH2)，2.22～2.15(m，2H，CH2)，1.53～1.48(m，2H，CH2)，1.45～1.41(m，2H，CH2)，1.32～1.26(m，4H，CH2)。
The unsaturated fluorocarbons prepared in examples 1-6 were subjected to radical polymerization with the same initiator, and the resulting polymers were tested for dielectric constant (Dk) and dielectric loss (Df), as shown in table 1, the dielectric constant and dielectric loss were measured according to GB1049-78(10 GHz).
TABLE 1
The unsaturated fluorocarbon prepared in the examples 1 to 6, the vinyl POSS and the C5 hydrocarbon resin are mixed according to the mass ratio of 6:1:3, the mixture is molded at a high temperature of 200 ℃ to prepare a plate, the thickness of the plate is 20-30 mm, the glass transition temperature, the mechanical property and the dielectric property of the prepared plate are tested, and the test results are shown in Table 2.
The glass transition temperature of the plate is tested by DSC, the bending strength of the plate is tested by GB1042-79 standard, the compressive strength is tested by GB1041-79 standard, the impact strength is tested by GB1043-79 standard, and the test method of the dielectric constant and the dielectric loss is GB1049-78(10 GHz).
TABLE 2
As can be seen from Table 1, the unsaturated fluorocarbon materials prepared in examples 1-6 have excellent dielectric properties and dielectric constants as low as 2.2C2/N·M2The dielectric loss can be as low as 2.8 x 10-4The performance is similar to that of the polytetrafluoroethylene material. The dielectric property of the fluorocarbon material is close to that of polytetrafluoroethylene, the melting point of the fluorocarbon material is 180-220 ℃, and the critical surface tension of the fluorocarbon material is 30-60 multiplied by 10-5N·cm-1The melting point and the surface tension of the composite board can meet the requirements of preparing the composite board.
As can be seen from Table 2, the performance of the sheet prepared by mixing the unsaturated fluorocarbon materials prepared in the examples 1 to 6 with other additives is similar to that of the conventional polytetrafluoroethylene sheet, and the sheet is more suitable for being applied to the technical field of 5G communication.
The epoxy resin adhesive and the single-layer board prepared by the method are used for preparing a multi-layer board, the number of layers of the board is 4, the thickness of the bonding layer is 100-200 mu m, the glass transition temperature, the mechanical property and the dielectric property of the 4-layer board are tested, and the test results are shown in table 3.
The glass transition temperature of the 4-layer plate is tested by DSC, the bending strength of the plate is tested by GB1042-79 standard, the compressive strength is tested by GB1041-79 standard, the impact strength is tested by GB1043-79 standard, and the test method of the dielectric constant and the dielectric loss is GB1049-78(10 GHz).
TABLE 3
The epoxy resin adhesive and the 4-layer plate prepared by the method are used for preparing the 8-layer plate, the thickness of the bonding layer is 100-200 mu m, the glass transition temperature, the mechanical property and the dielectric property of the 8-layer plate are tested, and the test results are shown in table 4.
The glass transition temperature of the 8-layer plate is tested by DSC, the bending strength of the plate is tested by GB1042-79 standard, the compressive strength is tested by GB1041-79 standard, the impact strength is tested by GB1043-79 standard, and the test method of the dielectric constant and the dielectric loss is GB1049-78(10 GHz).
TABLE 4
An epoxy resin adhesive and the 8-layer plate prepared by the method are used for preparing a 16-layer plate, the thickness of the bonding layer is 100-200 mu m, the glass transition temperature, the mechanical property and the dielectric property of the 8-layer plate are tested, and the test results are shown in table 5.
The glass transition temperature of the 16-layer plate is tested by DSC, the bending strength of the plate is tested by GB1042-79 standard, the compressive strength is tested by GB1041-79 standard, the impact strength is tested by GB1043-79 standard, and the test method of the dielectric constant and the dielectric loss is GB1049-78(10 GHz).
TABLE 5
From the test results in tables 3-5, it can be seen that the multilayer boards prepared from the single-layer boards prepared from the fluorocarbon compound of the present invention, i.e. the 4, 8 and 16 boards, all have excellent dielectric properties and mechanical properties, and are significantly improved compared with the single-layer boards. And the polytetrafluoroethylene single-layer board cannot be used for preparing a multi-layer board with stable performance, so that compared with a polytetrafluoroethylene board, the fluorocarbon provided by the invention can meet the requirement for preparing the multi-layer board.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (7)
1. An unsaturated fluorocarbon selected from the group consisting of:
2. The use of the unsaturated fluorocarbon compound of claim 1, wherein the unsaturated fluorocarbon compound is used for preparing bonding sheets, copper-clad plates and circuit boards.
3. The use according to claim 2, wherein the bonding sheet is prepared from a resin composition, the resin composition comprises the unsaturated fluorocarbon and/or fluorocarbon prepolymer and a hydrocarbon resin, or the resin composition comprises a fluorocarbon polymer and a hydrocarbon resin obtained by polymerization reaction of the unsaturated fluorocarbon and/or fluorocarbon prepolymer, wherein the fluorocarbon prepolymer is prepared from the unsaturated fluorocarbon through polymerization reaction.
4. The application of the copper-clad plate according to claim 3, wherein the preparation method of the copper-clad plate comprises the following steps: the resin composition is dispersed in a solvent to prepare a resin glue solution, the resin glue solution is coated on the surface of a substrate to obtain a prepreg plate, metal foils are attached to one side or two sides of the prepreg plate to obtain a copper-clad plate, or at least two layers of prepreg plates are overlapped to obtain a plurality of layers of prepreg plates, and the metal foils are attached to one side or two sides of the plurality of layers of prepreg plates to obtain the copper-clad plate.
5. The use according to claim 4, wherein the solvent is one or a mixture of at least two of acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, methanol, ethanol, ethylene glycol monomethyl ether, propylene glycol methyl ether acetate, ethyl acetate, N-dimethylformamide or N, N-diethylformamide.
6. The use according to claim 5, wherein the substrate is any one of a glass fiber substrate, a polyester substrate, a polyimide substrate, a ceramic substrate, or a carbon fiber substrate.
7. The application of the copper-clad plate as claimed in claim 6, wherein the circuit board is formed by processing circuits on the surface of the copper-clad plate.
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| US4029867A (en) * | 1971-02-22 | 1977-06-14 | The United States Of America As Represented By The Secretary Of Agriculture | Terpolymers of fluoroalkyl ethers and maleic anhydride |
| CN102010334A (en) * | 2010-10-25 | 2011-04-13 | 江苏梅兰化工有限公司 | Method for preparing fluorine-containing acrylate |
| CN108276863A (en) * | 2016-12-30 | 2018-07-13 | 东莞东阳光科研发有限公司 | A kind of novel three proofings e-coat agent |
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| US4029867A (en) * | 1971-02-22 | 1977-06-14 | The United States Of America As Represented By The Secretary Of Agriculture | Terpolymers of fluoroalkyl ethers and maleic anhydride |
| CN102010334A (en) * | 2010-10-25 | 2011-04-13 | 江苏梅兰化工有限公司 | Method for preparing fluorine-containing acrylate |
| CN108276863A (en) * | 2016-12-30 | 2018-07-13 | 东莞东阳光科研发有限公司 | A kind of novel three proofings e-coat agent |
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| Photopolymerized Low-Surface-Energy Coatings Based on a Novel Fluorinated Ether Acrylate;Bianca S. Shemper et al.;《Journal of Applied Polymer Science》;20040305;第91卷(第5期);第3301-3314页 * |
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