CN109534992A - A kind of unsaturation fluorocarbons and its preparation method and application - Google Patents
A kind of unsaturation fluorocarbons and its preparation method and application Download PDFInfo
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Abstract
The present invention provides a kind of unsaturated fluorocarbons and its preparation method and application.The polymer material that the unsaturation fluorocarbons is prepared has excellent dielectric properties and mechanical performance, and preparation process is simple, low in raw material price, can effectively reduce investment, reduce cost.
Description
Technical field
The invention belongs to polymer material field, it is related to a kind of unsaturated fluorocarbons and its preparation method and application.
Background technique
5G network is the 5th generation communication network, and performance has a matter compared to 4G network 4G network technology used today
Surmount.The progress of 5G network technology is significantly embodied in the side such as transmission timeliness, spreadability, communication secure of wireless signal
Face.5G network communication technology deeply combines other wireless mobile technologies, forms completely new communication network, and it is mobile to meet internet
Communicate the ever-increasing requirement of network speed.And 5G mobile network technology can also realize the intelligent phase intermodulation between automation
It is whole, there is certain flexibility, this is because the communication technology and wireless technology that we nowadays use are that 5G communication system is beaten
Good basis is descended.
The main target of 5G network is that terminal user is allowed to be in connected state always.The equipment that 5G network is supported in the future is much
Not just smart phone --- it will also support smartwatch, body building wrist strap, intelligent home equipment such as nest type room thermostat
Deng.5G network refers to next generation wireless network.5G network by be 4G network real upgrade version, its basic demand is distinct from
The wireless network of today.The transmission rate of the following 5G network is up to 10Gbps, it means that mobile phone user was in less than one second time
The downloading of a high-definition movie inside can be completed.
5G communication material requirements material has low-down dielectric constant and dielectric loss, and use is received in 4G communication now
Material mostly based on polytetrafluoroethylene (PTFE), by polytetrafluoroethylene (PTFE) be coated in copper foil on, reusing laser or chemical method makes to show
Coarse words, then bonded.But the multiple stratification ability of polytetrafluoroethylene material is poor, is not able to satisfy the base station 5G material multilayer
Requirement, while polytetrafluoroethylene material is usually large area production in the preparation, is difficult to manufacture the small material of size, application
Exist in 5G communication terminal and hinders.And the glass transition temperature of polytetrafluoroethylene (PTFE) is low, since powerful communications can produce
Raw amount of heat, therefore there is also defects for the stability of polytetrafluoroethylene (PTFE).
Summary of the invention
In order to solve the above technical problems, the present invention provides a kind of unsaturated fluorocarbons and its preparation method and application,
The polymer material that the unsaturation fluorocarbons is prepared has lower dielectric constant and dielectric loss, has simultaneously
There are excellent mechanical performance and heat resistance, is suitable for communication base station and terminal.
In order to achieve the above objectives, the invention adopts the following technical scheme:
It is an object of the present invention to provide a kind of unsaturated fluorocarbons, and the compound is by fluoracid and containing extremely
The compound of a few unsaturated group is prepared by intermolecular elimination reaction.
As preferred technical solution is invented, the fluorine content of the fluoracid is 25~67%, such as 25%, 30%, 35%,
40%, 45%, 50%, 55%, 60%, 65% or 67% etc., it is not limited to the numerical value solved, in the numberical range its
His unlisted numerical value is equally applicable.
In the present invention, fluoracid is preferably perfluor acid.
As preferred technical solution is invented, the fluoracid includes the fluoro-alkyl acid or pentafluoro benzoic acid of C2~C18,
It is excellent such as any one in C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17 or C18
It is selected as the perfluoroalkyl acid of C4~C10.
Hydrogen moiety in the present invention, in the linear or branched alkyl group acid that fluoro-alkyl acid is C2~C18 on alkyl chain
Or whole compound replaced fluorine atom.The present invention is preferably perfluor straight chained alkyl acid, structural formula F3C-(CF2)n-
COOH, the positive integer that wherein n is 0~16, preferably n=2~8.
As currently preferred technical solution, the compound for having at least one unsaturated group is to contain at least one
The compound of a hydroxyl, sulfydryl or carboxyl.
In the present invention, an active group is also at least contained in the compound containing at least one unsaturated group,
The active group can be hydroxyl, sulfydryl or carboxyl etc., it is not limited to above-mentioned group, can be and the carboxylic in perfluor acid
Any group that base reacts.Such as can be 4- vinyl benzoic acid, 2- methyl-1,4- dihydro benzoic acid, 5- vinyl-
2- pyridine carboxylic acid, butanol -3- alkene, 3- (3- alkene-butyl) phenol, hydroxyl dicyclopentadiene, octanol -7- alkene, 6,8- divinyl -
Any one in 2 naphthols or 4- (5- alkene-hexyl)-benzenethiol, it is not limited to above compound.
As currently preferred technical solution, the intermolecular elimination reaction include etherification reaction, thioetherification reaction or
Any one in esterification.
In the present invention, a intermolecular elimination reaction, that is, molecule small molecule compound is sloughed between compound A and compound B
The reaction of A-B compound is obtained, the small molecule can be water, hydrogen halides, hydrogen sulfide or methanol etc., and corresponding reaction can be
Etherification reaction, thioetherification reaction, esterification, amidation process or ester exchange reaction etc..
In the present invention, the typical but non-limiting structural formula of the compound has:
In any one.
The second purpose of the present invention is to provide a kind of preparation method of above-mentioned unsaturated fluorocarbons, the preparation methods
Are as follows: the chemical combination is prepared by intermolecular elimination reaction with the compound containing at least one unsaturated group in fluoracid
Object.
The three of the object of the invention are to provide a kind of fluorine carbon prepolymer, and the prepolymer wants above-mentioned unsaturated fluorine carbon by right
Compound is prepared by polymerization reaction.
The four of the object of the invention are to provide the application of the above-mentioned unsaturated fluorocarbons of one kind or fluorine carbon prepolymer, described
Unsaturated fluorocarbons or fluorine carbon prepolymer are used to prepare bonding sheet, copper-clad plate and wiring board.
As currently preferred technical solution, the bonding sheet is prepared by resin combination.
Preferably, the resin combination include the unsaturated fluorocarbons and/or the fluorine carbon prepolymer and
Hydrocarbon resin, or including the resin combination include the unsaturated fluorocarbons and/or the fluorine carbon prepolymer polymerization
React obtained fluorocarbon polymer and hydrocarbon resin.
In the present invention, the polymerization reaction is preferably free radical polymerization, free radical polymerization, that is, unsaturation provided by the invention
Under initiator effect, unsaturated bond (such as carbon-carbon double bond and triple carbon-carbon bonds) polymerize fluorocarbons.The free radical
Polymerization can be above-mentioned unsaturated fluorocarbons auto polymerization, is also possible to above-mentioned unsaturated fluorocarbons and contains not with other
The additive combined polymerization of saturated bond.
In the present invention, the fluorocarbons or fluorine carbon prepolymer are by the fluorocarbon polymer that polymerization reaction is prepared
Room temperature liquid or the solid-state for dissolving in solvent.It is liquid or soluble solid-state under the fluorocarbon polymer room temperature, so that described
Fluorocarbon polymer is easily worked, and is also easier to mix with other additions, is reduced processing cost.It is more readily available for making simultaneously small
Scale device, so that the material can be used for, mobile phone, laptop or tablet computer etc. be small-sized or the system of Miniaturized Communications terminal
Make.
As currently preferred technical solution, the copper-clad plate the preparation method comprises the following steps: the resin combination is scattered in
Be prepared resin adhesive liquid in solvent, the resin adhesive liquid is coated on substrate surface and obtains pre-impregnated sheet, the pre-impregnated sheet it is unilateral or
Two sides fitting metal foil obtains copper-clad plate, or at least two layers of pre-impregnated sheet overlaps to obtain multilayer pre-impregnated sheet, with the multilayer pre-impregnated sheet
Unilateral or two sides fitting metal foil obtains copper-clad plate.
Preferably, the solvent is one of ketone, hydro carbons, ethers, esters or aprotic solvent or at least two
Combination, preferably acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), toluene, dimethylbenzene, methanol, ethyl alcohol, primary alconol, ethylene glycol list first
Ether, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, ethyl acetate, N,N-dimethylformamide or N, N- diethylformamide
One of or at least two mixture, the combination is typical but non-limiting example has: acetone and methyl ethyl ketone
Combination, methyl ethyl ketone and the combination of methyl iso-butyl ketone (MIBK), the combination of toluene and dimethylbenzene, methanol and ethyl alcohol combination, ethyl alcohol
The combination of combination, glycol monoethyl ether and propylene glycol monomethyl ether with isopropanol, propylene glycol methyl ether acetate and ethyl acetate
It combines, combination or the methanol, glycol monoethyl ether and methyl ethyl ketone of N,N-dimethylformamide and N, N- diethylformamide
Combination.
Preferably, the substrate is fiberglass substrate, polyester base material, polyimide base material, ceramic base material or carbon fiber
Any one in substrate.
Preferably, the wiring board is formed by copper-clad plate surface processing line.
Fluorocarbons or fluorine carbon prepolymer provided by the invention has by the fluorocarbon polymer that polymerization reaction is prepared
There are extremely low dielectric constant and dielectric loss, meets the 5G communication technology for material on dielectric constant and dielectric loss
It is required that while the communication material have good heat resistance and mechanical performance, be more suitable for the system of high-power communication equipment
Make.
In the present invention, the unsaturated fluorocarbons provided can mix altogether with raw materials such as vinyl POSS, hydrocarbon resins
It is poly-, also can be used the material obtained after unsaturated fluorocarbons or fluorine carbon prepolymer free radical polymerization and vinyl POSS,
The mixing of the raw materials such as hydrocarbon resin, the plate that above two mixture high-temperature molding is prepared have excellent mechanically performance
And dielectric properties, the construction suitable for 5G communication base station.
Moreover, since the fusing point of polytetrafluoroethylene (PTFE) is up to 327 DEG C so that its in terms of processing there are many difficulties,
And the critical surface tension of polytetrafluoroethylene (PTFE) is only 18 × 10-5N·cm-1, and the adhesive used in multiple-plate preparation
Tension is greater than 18 × 10-5N·cm-1, it is unfavorable for adhesive in the even spread of ptfe surface, therefore polytetrafluoro
Although vinyl material has good dielectric properties, it is difficult to multiple-plate preparation.Since high-frequency high-speed communicates, especially
The signal transmission power for being 5G communication will be much higher than the existing 4G communication technology, since the volume of base station and communication equipment has
Limit, therefore single plate material is to be difficult meet demand, it is necessary to which multilayer circuit board improves the area of route, to improve transmitting function
Rate.Fluorocarbon material provided by the invention, close in dielectric properties and polytetrafluoroethylene material, can satisfy high-frequency high-speed communication needs
Under the premise of asking, there is lower fusing point and higher critical surface tension compared to polytetrafluoroethylene (PTFE), be suitable for multi-layer board
Production.
Compared with prior art, the present invention at least has the advantages that
(1) present invention provides a kind of unsaturated fluorocarbons, and the compound, which polymerize to obtain high-molecular compound, to be had
Excellent dielectric properties, dielectric constant can be down to 2.2C2/N·M2, dielectric loss can be down to 2.9 × 10-4, it is suitable for 5G and communicates
Equal high frequencies high-speed communication field；
(2) present invention provides a kind of unsaturated fluorocarbons, and the compound is prepared into after mixing with other additives
The plate arrived has excellent mechanical performance and dielectric properties, and performance is better than traditional polytetrafluoroethylene (PTFE) plate comprehensively, more applicable
In the construction of 5G communication base station；
(3) present invention provides a kind of unsaturated fluorocarbons, and the compound is in dielectric properties and polytetrafluoroethylene (PTFE) material
Material is close, under the premise of can satisfy high-frequency high-speed communication requirement, compared to polytetrafluoroethylene (PTFE) with lower fusing point and more
High critical surface tension is suitable for multiple-plate production.
Specific embodiment
Of the invention for ease of understanding, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is only to aid in the understanding present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
The present invention provides a kind of unsaturated fluorocarbons, and structure is shown in formula I:
Compound shown in Formulas I the preparation method comprises the following steps: 1mol perfluor lauric acid/dodecanoic acid is mixed with 1.2mol 4- vinyl-benzyl alcohol,
0.1mol/L sodium hydroxide solution 100mL is added, mechanical stirring heats reaction 2h at 80 DEG C, is cooled to room temperature, 500mL washing
5 times, anhydrous sodium sulfate is added in liquid separation, stands 2h, and filtering obtains compound shown in Formulas I.
1H NMR(CDCl3, 500MHz): δ 7.67~7.61 (m, 2H, Ar-H), 7.35~7.27 (m, 2H, Ar-H), 6.66
~6.60 (m, H, CH2=CH), 5.63~5.57 (t, H, CH 2=CH), 5.25~5.19 (s, 2H, CH2), 5.21~5.16 (t,
H, CH 2=CH).
Embodiment 2
The present invention provides a kind of unsaturated fluorocarbons, and structure is as shown in Formula II:
Compound shown in Formula II the preparation method comprises the following steps: 1mol perfluorobutyric acid and 1.2mol 2- methyl-1,4- dihydro benzyl alcohol
0.1mol/L sodium hydroxide solution 100mL is added in mixing, and mechanical stirring heats reaction 2.5h at 80 DEG C, is cooled to room temperature,
500mL is washed 5 times, liquid separation, and anhydrous sodium sulfate is added, and stands 2h, and filtering obtains compound shown in Formula II.
1H NMR(CDCl3, 500MHz): δ 5.88~5.82 (m, H, CH=CH), 5.41~5.35 (m, H, CH=CH),
5.22~5.18 (t, H, CH=C), 4.28~4.22 (s, 2H, CH2), 3.48~3.42 (d, H, CH), 2.69~2.60 (t,
2H, CH2), 1.85~1.80 (t, 3H, CH3)。
Embodiment 3
The present invention provides a kind of unsaturated fluorocarbons, and structure is represented by a formula X:
Compound shown in formula III the preparation method comprises the following steps: 1.2mol perfluoro caprylic acid is mixed with 1mol methallyl alcohol, be added dense
Sulfuric acid 20mL, mechanical stirring are heated to back flow reaction 2.5h, are cooled to room temperature, and 500mL is washed 5 times, liquid separation, and anhydrous slufuric acid is added
Sodium, stands 2h, and filtering obtains compound shown in formula III.
1H NMR(CDCl3, 500MHz): δ 5.35~5.30 (s, H, CH2=C), 5.21~5.15 (s, H, CH2=C),
4.78~4.72 (s, 2H, CH2), 1.85~1.79 (s, 3H, CH3)。
Embodiment 4
The present invention provides a kind of unsaturated fluorocarbons, and structure is as shown in formula IV:
Compound shown in formula IV the preparation method comprises the following steps: 1mol perfluor caproic acid is mixed with 1.1mol butanol -3- alkene, be added
0.1mol/L sodium hydroxide solution 100mL, mechanical stirring heat reaction 2h at 75 DEG C, are cooled to room temperature, and 500mL is washed 5 times,
Anhydrous sodium sulfate is added in liquid separation, stands 2h, and filtering obtains compound shown in formula IV.
1H NMR(CDCl3, 500MHz): δ 5.73~5.68 (m, H, CH2=CH), 5.05~4.95 (t, 2H, CH 2=
CH), 4.15~4.08 (t, 2H, CH2), 2.25~2.17 (m, 2H, CH2)。
Embodiment 5
The present invention provides a kind of unsaturated fluorocarbons, and structure is shown as a formula V:
Compound shown in Formula V the preparation method comprises the following steps: 1mol perfluoro-pelargonic acid is mixed with 1.2mol phenol, 0.1mol/L hydrogen is added
Sodium hydroxide solution 100mL, mechanical stirring heat reaction 2h at 75 DEG C, are cooled to room temperature, and 500mL is washed 5 times, liquid separation, is added
Anhydrous sodium sulfate stands 2h, filtering, and obtained solid is mixed with the chloro- 1- butylene of 1mol4-, addition 0.1mol alchlor, and 60
DEG C reaction 1.5h, be cooled to room temperature, 500mL wash 5 times, liquid separation, be added anhydrous sodium sulfate, stand 2h, filtering, obtain Formula V institute
Show compound.
1H NMR(CDCl3, 500MHz): δ 7.23~7.15 (m, H, Ar-H), 6.95~6.85 (m, 3H, Ar-H), 5.73
~5.65 (m, H, CH2=CH), 5.06~4.95 (t, H, CH 2=CH), 2.63~2.57 (t, H, CH2), 2.33~2.28 (m,
2H, CH2)。
Embodiment 6
The present invention provides a kind of unsaturated fluorocarbons, and structure is as shown in Formula IV:
Compound shown in Formula IV the preparation method comprises the following steps: 1mol perfluor stearic acid is mixed with 1.3mol hydroxyl dicyclopentadiene,
0.1mol/L sodium hydroxide solution 100mL is added, mechanical stirring heats reaction 3h at 80 DEG C, is cooled to room temperature, 500mL ethyl alcohol
It washes 5 times, liquid separation, is evaporated under reduced pressure residual ethanol, obtains compound shown in Formula IV.
1H NMR(CDCl3, 500MHz): δ 5.64~5.58 (m, 2H, CH=CH), 3.92~3.86 (t, H, CH), 2.28
~2.22 (t, 2H, CH2), 2.12~2.03 (m, 2H, CH), 1.51~1.40 (m, 2H, CH2), 1.38~1.32 (t, 2H,
CH2)。
Under the effect of identical initiator, radical polymerization is carried out to the unsaturated fluorocarbons that embodiment 1-6 is prepared
It closes, the dielectric constant (Dk) and dielectric loss (Df) of obtained polymer is tested, the results are shown in Table 1, and dielectric is normal
Several and dielectric loss test method is GB1049-78 (10GHz),.
Table 1
The unsaturated fluorocarbons and vinyl POSS and C5 hydrocarbon resin that embodiment 1-6 is prepared are according to quality
It is mixed than 6:1:3, plate is made in 200 DEG C of high-temperature moldings, and 20~30mm of plate thickness turns the vitrifying for the plate being prepared
Temperature, mechanical performance and dielectric properties are tested, and test result is as shown in table 2.
The glass transition temperature of plate is tested using DSC, the bending strength of plate using GB1042-79 standard into
Row test, compression strength are tested using GB1041-79 standard, and impact strength is tested using GB1043-79, dielectric
The test method of constant and dielectric loss is GB1049-78 (10GHz).
Table 2
As it can be seen from table 1 free radical polymerization preparation occurs for the unsaturated fluorocarbon material itself that embodiment 1-6 is prepared
Obtained material has excellent dielectric properties, and dielectric constant can be down to 2.2C2/N·M2, dielectric loss can be down to 2.8 × 10-4, performance is close with polytetrafluoroethylene material.It is same similar in offer fluorocarbon material dielectric properties and polytetrafluoroethylene (PTFE) of the invention
When, fusing point is between 180~220 DEG C, and critical surface tension is 30~60 × 10-5N·cm-1Between, fusing point and surface
Tension, which is able to satisfy, prepares multiple-plate demand.
From table 2 it can be seen that unsaturated fluorocarbon material and other additives that embodiment 1-6 is prepared are mixed with
The plate arrived, performance is close with traditional polytetrafluoroethylene (PTFE) plate, is more suitably applied to 5G field of communication technology.
Multi-layer board is prepared using epoxyn and the above-mentioned lamina being prepared, the number of plies of plate is 4, bonding
Layer carries out the glass transition temperature for 4 laminates being prepared, mechanical performance and dielectric properties with a thickness of 100~200 μm
Test, test result are as shown in table 3.
The glass transition temperature of 4 laminates is tested using DSC, and the bending strength of plate uses GB1042-79 standard
It is tested, compression strength is tested using GB1041-79 standard, and impact strength is tested using GB1043-79, is situated between
The test method of electric constant and dielectric loss is GB1049-78 (10GHz).
Table 3
8 laminates are prepared using epoxyn and above-mentioned 4 laminates that are prepared, adhesive layer thickness is 100~
200 μm, the glass transition temperature for 8 laminates being prepared, mechanical performance and dielectric properties are tested, test result
As shown in table 4.
The glass transition temperature of 8 laminates is tested using DSC, and the bending strength of plate uses GB1042-79 standard
It is tested, compression strength is tested using GB1041-79 standard, and impact strength is tested using GB1043-79, is situated between
The test method of electric constant and dielectric loss is GB1049-78 (10GHz).
Table 4
16 laminates are prepared using epoxyn and above-mentioned 8 laminates that are prepared, adhesive layer thickness is 100~
200 μm, the glass transition temperature for 8 laminates being prepared, mechanical performance and dielectric properties are tested, test result
As shown in table 5.
The glass transition temperature of 16 laminates is tested using DSC, and the bending strength of plate uses GB1042-79 standard
It is tested, compression strength is tested using GB1041-79 standard, and impact strength is tested using GB1043-79, is situated between
The test method of electric constant and dielectric loss is GB1049-78 (10GHz).
Table 5
Can be seen that the lamina being prepared using fluorocarbons of the present invention from the test result of table 3-5 and
The multi-layer board being prepared, i.e., the plate of 4,8 and 16 all have excellent dielectric properties and mechanical performance, and have compared to lamina
Significantly improve.And polytetrafluoroethylene (PTFE) lamina can not the stable multi-layer board of processability, therefore compare polytetrafluoroethylene (PTFE)
Plate, fluorocarbons provided by the invention, which is more able to satisfy, prepares multiple-plate demand.
The Applicant declares that the present invention is explained by the above embodiments detailed process equipment and process flow of the invention,
But the present invention is not limited to the above detailed process equipment and process flow, that is, it is above-mentioned detailed not mean that the present invention must rely on
Process equipment and process flow could be implemented.It should be clear to those skilled in the art, any improvement in the present invention,
Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within of the invention
Within protection scope and the open scope.
Claims (10)
1. a kind of unsaturation fluorocarbons, which is characterized in that the compound is unsaturated by fluoracid and containing at least one
The compound of group is prepared by intermolecular elimination reaction.
2. compound according to claim 1, which is characterized in that the fluorine content of the fluoracid is 25~67%.
3. compound according to claim 2, which is characterized in that the fluoracid includes the fluoro-alkyl acid of C2~C18
Or pentafluoro benzoic acid, the preferably fluoracid of C4~C10.
4. compound according to claim 1-3, which is characterized in that described to contain at least one unsaturated group
Compound be the compound containing at least one hydroxyl, sulfydryl or carboxyl.
5. compound according to claim 1-4, which is characterized in that the intermolecular elimination reaction is that esterification is anti-
It answers.
6. a kind of preparation method of any one of claim 1-5 compound, which is characterized in that the preparation method is that: fluorine
The compound is prepared by intermolecular elimination reaction with the compound containing at least one unsaturated group in generation acid.
7. a kind of fluorine carbon prepolymer, which is characterized in that the prepolymer is by the described in any item unsaturated fluorine carbon of claim 1-5
Compound is prepared by polymerization reaction.
8. a kind of described in any item unsaturated fluorocarbons of claim 1-5 or fluorine carbon prepolymer as claimed in claim 7
Application, which is characterized in that the fluorocarbons or fluorine carbon prepolymer are used to prepare bonding sheet, copper-clad plate and wiring board.
9. application according to claim 8, which is characterized in that the bonding sheet is prepared by resin combination；
Preferably, the resin combination includes the unsaturated fluorocarbons and/or the fluorine carbon prepolymer and hydrocarbon
Resin or the resin combination include that the unsaturated fluorocarbons and/or the fluorine carbon prepolymer polymerization react to obtain
Fluorocarbon polymer and hydrocarbon resin.
10. application according to claim 8, which is characterized in that the copper-clad plate the preparation method comprises the following steps: the resin combination
Object, which is scattered in solvent, is prepared resin adhesive liquid, and the resin adhesive liquid is coated on substrate surface and obtains pre-impregnated sheet, the preimpregnation
Plate is unilateral or two sides fitting metal foil obtains copper-clad plate, or at least two layers of pre-impregnated sheet overlaps to obtain multilayer pre-impregnated sheet, and described more
Layer pre-impregnated sheet is unilateral or two sides fitting metal foil obtains copper-clad plate；
Preferably, the solvent is the group of one of ketone, hydro carbons, ethers, esters or aprotic solvent or at least two
Close, preferably acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), toluene, dimethylbenzene, methanol, ethyl alcohol, primary alconol, glycol monoethyl ether,
Propylene glycol monomethyl ether, propylene glycol methyl ether acetate, ethyl acetate, N,N-dimethylformamide or N, in N- diethylformamide
It is a kind of or at least two mixture；
Preferably, the substrate is fiberglass substrate, polyester base material, polyimide base material, ceramic base material or carbon fiber base material
In any one；
Preferably, the wiring board is formed by copper-clad plate surface processing line.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4707076A (en) * | 1985-04-12 | 1987-11-17 | Ensign-Bickford Industries, Inc. | Coating compositions for optical fibers |
| CN1856522A (en) * | 2003-09-25 | 2006-11-01 | 西巴特殊化学品控股有限公司 | ROMP with fluorinated groups |
| WO2016014952A1 (en) * | 2014-07-25 | 2016-01-28 | University Of Florida Research Foundation, Inc. | Superhydrophobic and oleophobic ceramic polymer composite coating |
-
2018
- 2018-11-15 CN CN201811359494.7A patent/CN109534992B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4707076A (en) * | 1985-04-12 | 1987-11-17 | Ensign-Bickford Industries, Inc. | Coating compositions for optical fibers |
| CN1856522A (en) * | 2003-09-25 | 2006-11-01 | 西巴特殊化学品控股有限公司 | ROMP with fluorinated groups |
| WO2016014952A1 (en) * | 2014-07-25 | 2016-01-28 | University Of Florida Research Foundation, Inc. | Superhydrophobic and oleophobic ceramic polymer composite coating |
Non-Patent Citations (1)
| Title |
|---|
| 周晓东等: "对甲苯磺酸催化合成全氟辛酸烯丙酯", 《有机氟工业》 * |
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