CN116023574B - Polytetrafluoroethylene dispersion for copper-clad plate and its preparation method - Google Patents
Polytetrafluoroethylene dispersion for copper-clad plate and its preparation method Download PDFInfo
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- CN116023574B CN116023574B CN202111250306.9A CN202111250306A CN116023574B CN 116023574 B CN116023574 B CN 116023574B CN 202111250306 A CN202111250306 A CN 202111250306A CN 116023574 B CN116023574 B CN 116023574B
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- -1 Polytetrafluoroethylene Polymers 0.000 title claims abstract description 99
- 229920001343 polytetrafluoroethylene Polymers 0.000 title claims abstract description 87
- 239000004810 polytetrafluoroethylene Substances 0.000 title claims abstract description 87
- 239000006185 dispersion Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000007787 solid Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- 239000003999 initiator Substances 0.000 claims description 24
- 238000006116 polymerization reaction Methods 0.000 claims description 21
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 20
- 239000003995 emulsifying agent Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 17
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 16
- 239000002270 dispersing agent Substances 0.000 claims description 15
- 239000003607 modifier Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 12
- 239000012188 paraffin wax Substances 0.000 claims description 12
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 11
- 229910052731 fluorine Inorganic materials 0.000 claims description 11
- 239000011737 fluorine Substances 0.000 claims description 11
- 239000003381 stabilizer Substances 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 10
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 10
- 150000003333 secondary alcohols Chemical class 0.000 claims description 9
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 7
- 229920000570 polyether Polymers 0.000 claims description 7
- GVEUEBXMTMZVSD-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,6-nonafluorohex-1-ene Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C=C GVEUEBXMTMZVSD-UHFFFAOYSA-N 0.000 claims description 6
- MKTOIPPVFPJEQO-UHFFFAOYSA-N 4-(3-carboxypropanoylperoxy)-4-oxobutanoic acid Chemical compound OC(=O)CCC(=O)OOC(=O)CCC(O)=O MKTOIPPVFPJEQO-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 150000007942 carboxylates Chemical class 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- YOALFLHFSFEMLP-UHFFFAOYSA-N azane;2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoic acid Chemical group [NH4+].[O-]C(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YOALFLHFSFEMLP-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 125000005210 alkyl ammonium group Chemical group 0.000 claims description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 150000002978 peroxides Chemical group 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- 239000003002 pH adjusting agent Substances 0.000 claims 1
- 238000010979 pH adjustment Methods 0.000 claims 1
- 230000005484 gravity Effects 0.000 abstract description 6
- 238000012545 processing Methods 0.000 abstract description 4
- 238000003860 storage Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 18
- 239000007864 aqueous solution Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000000839 emulsion Substances 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000007792 addition Methods 0.000 description 6
- 239000000945 filler Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000003490 calendering Methods 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- BLTXWCKMNMYXEA-UHFFFAOYSA-N 1,1,2-trifluoro-2-(trifluoromethoxy)ethene Chemical compound FC(F)=C(F)OC(F)(F)F BLTXWCKMNMYXEA-UHFFFAOYSA-N 0.000 description 1
- WUMVZXWBOFOYAW-UHFFFAOYSA-N 1,2,3,3,4,4,4-heptafluoro-1-(1,2,3,3,4,4,4-heptafluorobut-1-enoxy)but-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)=C(F)OC(F)=C(F)C(F)(F)C(F)(F)F WUMVZXWBOFOYAW-UHFFFAOYSA-N 0.000 description 1
- DAVCAHWKKDIRLY-UHFFFAOYSA-N 1-ethenoxy-1,1,2,2,3,3,3-heptafluoropropane Chemical compound FC(F)(F)C(F)(F)C(F)(F)OC=C DAVCAHWKKDIRLY-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- AIQGDKGGGMYKDA-UHFFFAOYSA-N FC(C(C(C(F)(F)F)(C(F)(F)F)F)(F)F)(C(=C(F)F)Cl)F Chemical compound FC(C(C(C(F)(F)F)(C(F)(F)F)F)(F)F)(C(=C(F)F)Cl)F AIQGDKGGGMYKDA-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000003311 flocculating effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- URXNVXOMQQCBHS-UHFFFAOYSA-N naphthalene;sodium Chemical compound [Na].C1=CC=CC2=CC=CC=C21 URXNVXOMQQCBHS-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention provides polytetrafluoroethylene dispersion for a copper-clad plate and a preparation method thereof. The polytetrafluoroethylene dispersion prepared by the method has the solid content of 25-30%, the Standard Specific Gravity (SSG) of 2.167-2.173, and the polytetrafluoroethylene dispersion is a green environment-friendly product, has good storage stability, and meanwhile, the polytetrafluoroethylene copper-clad plate prepared by application and processing has good sheet formability, good appearance color, low dielectric loss factor and other excellent comprehensive properties.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to polytetrafluoroethylene dispersion for a copper-clad plate and a preparation method thereof.
Background
Polytetrafluoroethylene has excellent chemical corrosion resistance, high and low temperature resistance, aging resistance, low friction, non-tackiness and physiological inertia, so that the polytetrafluoroethylene becomes an indispensable special material in the fields of chemical industry, machinery, electricity, construction, medical treatment and the like. Polytetrafluoroethylene materials have excellent dielectric properties (lower dielectric constant and dielectric loss, etc.), as well as good chemical and thermal stability. With the gradual development of communication and electronic products to high frequency and high speed, the market demand of PTFE copper clad laminate is rapidly increased, and the PTFE copper clad laminate is widely applied to the manufacturing industries of communication equipment, computers, automobile electronics, household appliances and the like. In the high frequency substrate industry, the dielectric constant, dielectric loss, water absorption and frequency characteristics of the PTFE copper-clad plate are all the best.
Patent CN201711456721.3 discloses a method for manufacturing a modified polytetrafluoroethylene copper-clad plate. The method comprises the following steps: (1) Modifying the sodium-naphthalene treated polytetrafluoroethylene by adopting a grafting monomer to obtain modified polytetrafluoroethylene; (2) Modifying the filler by adopting a coupling agent to obtain modified filler; (3) Dispersing the modified polytetrafluoroethylene obtained in the step (1) in kerosene, then adding the modified filler obtained in the step (2), and mixing to obtain slurry; (4) And (3) coating the copper foil by adopting the slurry in the step (3), and pressing to obtain the modified polytetrafluoroethylene copper-clad plate. The method adopts polytetrafluoroethylene powder, and the preparation method of polytetrafluoroethylene is not described.
Patent CN201910316897.1 discloses a preparation method of polytetrafluoroethylene copper-clad plate. The preparation method comprises the following steps: 1. uniformly mixing raw material components including polytetrafluoroethylene powder, a lubricant, ceramic powder and short glass fibers, and curing; 2. molding to obtain a preform; 3. obtaining a green sheet by calendaring, and then drying; 4. and covering copper foil on two sides of the green substrate, sintering, maintaining the pressure, and cooling to room temperature to obtain the polytetrafluoroethylene copper-clad plate. The invention replaces the preparation mode of sizing and dipping by PTFE dispersion liquid, eliminates the harm of toxic fluoride, nitrogen oxide and the like, has good filler dispersion effect, is uniformly mixed, and has good dimensional stability of products. Through reasonable proportion, the prepared PTFE copper-clad plate has different dielectric constants of 2.6-8.6MHz, dielectric loss factor not more than 0.003, peel strength not less than 1.7kN/m and comprehensive performance meeting the use requirement. The invention has simple process and meets the requirement of industrialized mass production. The method adopts polytetrafluoroethylene powder, and the method for preparing polytetrafluoroethylene is not described.
Patent CN110172165a discloses a preparation method of silica filled polytetrafluoroethylene dispersion, which improves interfacial binding force between filler and polytetrafluoroethylene by dispersing and mixing the filler and polytetrafluoroethylene in a liquid medium, improves surface defects in the impregnation process, is suitable for impregnating glass cloth, and is used for producing high-performance polytetrafluoroethylene copper-clad plates; the method effectively solves the defects of large thermal expansion coefficient, poor wear resistance, low mechanical strength and the like of the traditional copper-clad plate, improves the precipitation problem of inorganic fillers, and remarkably improves the uniformity of glue components. The method does not describe the preparation of polytetrafluoroethylene emulsion.
Disclosure of Invention
The invention provides a preparation method of polytetrafluoroethylene dispersion for a copper-clad plate, which comprises the following steps:
1) Adding a modifier, a tetrafluoroethylene monomer and an initiator into a reaction kettle containing deionized water, a dispersing agent and a stabilizing agent, wherein the content of internal oxygen is not more than 30ppm, controlling the temperature of polymerization reaction to be 74+/-1 ℃ and the pressure to be 2.2-2.8Mpa, and obtaining polytetrafluoroethylene polymerization solution with the solid content of 29-31%;
2) Adding an emulsifier and a pH regulator into the polytetrafluoroethylene polymerization solution to obtain polytetrafluoroethylene dispersion;
the modifier is perfluoroalkyl olefin or perfluoroalkyl vinyl ether, and the dosage of the modifier is 0.003-0.011% of the mass of deionized water;
the emulsifier is an environment-friendly nonionic surfactant, and the dosage of the emulsifier is 2-3% of the dry polytetrafluoroethylene material.
The invention discovers that in the polymerization process, the modifier is added, and the polymerization reaction is controlled to be carried out in the constant temperature mode, so that the emulsion primary particle size distribution is controlled, the uniformity of the primary particle form is ensured, the size is moderate, the strength of the polytetrafluoroethylene copper-clad plate product is improved, and the mechanical processing performance of the polytetrafluoroethylene copper-clad plate product is ensured; meanwhile, the solid content of the polytetrafluoroethylene polymer is controlled to be 29-31%, and in the post-treatment process of the emulsion, the emulsifier with the dosage ensures that the prepared polytetrafluoroethylene dispersion is stable and does not settle for a certain time, has good storage stability, and meanwhile, the emulsifier is free from residue in the processing process of the polytetrafluoroethylene copper-clad plate product, so that the product has excellent comprehensive properties, such as good appearance color, good formability, low dielectric loss factor and the like.
Preferably, the modifier is selected from one or more of perfluoropropylene, trifluorochloroethylene, vinylidene fluoride, perfluorobutyl ethylene, perfluoromethyl vinyl ether, perfluoroethyl vinyl ether and perfluoro-n-propyl vinyl ether, and further preferably perfluorobutyl ethylene;
the modifier is used in an amount of 0.003-0.0095% of the mass of deionized water.
Preferably, the emulsifier is isomeric alcohol polyoxyethylene ether and/or secondary alcohol polyoxyethylene ether, and further preferably branched secondary alcohol polyoxyethylene ether;
the dosage of the emulsifier is 2.3-2.7% of the dry polytetrafluoroethylene material.
Preferably, the deionized water is used in an amount of 50-70% by volume of the reaction vessel, more preferably 60-70%.
Preferably, the tetrafluoroethylene monomer is added in the form of a gaseous tetrafluoroethylene monomer, and the addition amount of the tetrafluoroethylene monomer is 40-60% by mass of deionized water, and more preferably 45-57%.
Preferably, the dispersing agent is ammonium perfluorooctanoate substitute; further preferred are one or more of perfluoro or fluorine-containing polyether carboxylate, perfluoro or fluorine-containing alkyl ammonium carboxylate or salt thereof, perfluoro or fluorine-containing alkyl ammonium sulfonate or salt thereof; more preferably perfluoro or fluoropolyether carboxylate;
the dispersant is used in an amount of 0.01 to 0.15% by mass, preferably 0.05 to 0.1% by mass, based on the mass of deionized water.
According to the invention, the ammonium perfluorooctanoate substitute is used as a dispersing agent, and an environment-friendly emulsifier is used in the post-treatment process, so that the prepared polytetrafluoroethylene dispersion is an environment-friendly product, and the comprehensive usability of the product is further improved.
Preferably, the stabilizer is solid paraffin or saturated hydrocarbon with carbon number more than or equal to 12; further preferably, the solid paraffin is provided, and the melting point of the solid paraffin is 56-58 ℃;
the stabilizer is used in an amount of 1.0-8.0% by mass, preferably 3.0-6.0% by mass, of deionized water.
Preferably, the initiator is an inorganic initiator and/or an organic initiator; the inorganic initiator is persulfate of alkali metal, preferably one or two of ammonium persulfate and potassium persulfate; the organic initiator is peroxide, preferably one or two of benzoyl peroxide and succinic acid peroxide;
the initiator is preferably succinic peroxide, and the initiator is used in an amount of 0.01-0.07% by mass, preferably 0.02-0.05% by mass, of deionized water.
Preferably, the pH regulator is selected from one or more of sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide and ammonia water, and further preferably tetramethylammonium hydroxide, thereby avoiding the generation of pungent odor substances and creating a good environment.
The invention also provides polytetrafluoroethylene dispersion for the copper-clad plate, which is prepared by the method.
The invention has the beneficial effects that:
the polytetrafluoroethylene dispersion prepared by the method has the solid content of 25-30%, the Standard Specific Gravity (SSG) of 2.167-2.173, and the polytetrafluoroethylene dispersion is a green environment-friendly product, has good storage stability, and meanwhile, the polytetrafluoroethylene copper-clad plate prepared by application and processing has good sheet formability, good appearance color, low dielectric loss factor and other excellent comprehensive properties.
Detailed Description
The following examples are illustrative of the invention and are not intended to limit the scope of the invention.
The specific techniques or conditions are not identified in the examples and are described in the literature in this field or are carried out in accordance with the product specifications. The reagents or equipment used were conventional products available for purchase by regular vendors without the manufacturer's attention.
Example 1
The embodiment provides a preparation method of polytetrafluoroethylene dispersion for a copper-clad plate, which comprises the following steps:
1) A50L stainless steel high-pressure reaction kettle is cleaned, 32L of 16MΩ high-purity deionized water, 8g of dispersing agent fluorine-containing polyether ammonium carboxylate and 2kg of stabilizer paraffin are added, the kettle is closed, the kettle is evacuated and replaced by nitrogen, and then the oxygen content is analyzed, and the kettle is qualified when the oxygen content is less than or equal to 30 ppm. And 2g of modifier perfluorobutyl ethylene is added after oxygen analysis is qualified. The reaction kettle is heated to 72 ℃, gaseous monomer tetrafluoroethylene is added until the pressure in the kettle is 2.5MPa, and 2L of aqueous solution containing 10g (pure) of succinic peroxide as an initiator is added through a metering pump. The pressure in the reactor is maintained at 2.5MPa and the temperature is 74+/-1 ℃. The initiator may be appropriately added according to the polymerization rate, and the number of additions depends on the reaction rate. When the feeding amount of the tetrafluoroethylene reaches 3Kg, 1L of aqueous solution containing 42g of residual dispersing agent fluorine-containing polyether ammonium carboxylate is continuously and uniformly added into the polymerization system, and when the feeding amount of the tetrafluoroethylene reaches 8Kg, the adding is completed. When the feeding amount of the tetrafluoroethylene reaches 17Kg, the reaction is finished, the gas phase monomer is recovered, the temperature is reduced, the discharging is carried out, and paraffin is separated, so that polytetrafluoroethylene polymerization solution with the solid content of about 31% is obtained.
2) Adding branched secondary alcohol polyoxyethylene ether serving as an emulsifier and accounting for 2.5% of the dry polytetrafluoroethylene material into the obtained polytetrafluoroethylene polymerization solution, stirring at a low speed of 10r/min in a dosing tank for 1.5-2 hours, adding a pH regulator tetramethylammonium hydroxide aqueous solution to adjust the pH value to about 8 (measured by pH test paper), and adjusting the specific gravity of the emulsion to obtain polytetrafluoroethylene dispersion with 30% of solid content.
Example 2
The embodiment provides a preparation method of polytetrafluoroethylene dispersion for a copper-clad plate, which comprises the following steps:
1) A50L stainless steel high-pressure reaction kettle is cleaned, 32L of 16MΩ high-purity deionized water, 50g of dispersing agent fluorine-containing polyether ammonium carboxylate and 2kg of stabilizer paraffin are added, the kettle is closed, the kettle is evacuated and replaced by nitrogen, and then the oxygen content is analyzed, and the kettle is qualified when the oxygen content is less than or equal to 30 ppm. And 2g of modifier perfluorobutyl ethylene is added after oxygen analysis is qualified. The reaction kettle is heated to 72 ℃, gaseous monomer tetrafluoroethylene is added until the pressure in the kettle is 2.5MPa, and 2L of aqueous solution containing 10g (pure) of succinic peroxide as an initiator is added through a metering pump. The pressure in the reactor is maintained at 2.5MPa and the temperature is 74+/-1 ℃. The initiator may be appropriately added according to the polymerization rate, and the number of additions depends on the reaction rate. When the feeding amount of the tetrafluoroethylene reaches 17Kg, the reaction is finished, the gas phase monomer is recovered, the temperature is reduced, the discharging is carried out, and paraffin is separated, so that polytetrafluoroethylene polymerization solution with the solid content of about 31% is obtained.
2) Adding branched secondary alcohol polyoxyethylene ether serving as an emulsifier and accounting for 2.5% of the dry polytetrafluoroethylene material into the obtained polytetrafluoroethylene polymerization solution, stirring at a low speed of 10r/min in a dosing tank for 1.5-2 hours, adding a pH regulator tetramethylammonium hydroxide aqueous solution to adjust the pH value to about 8 (measured by pH test paper), and adjusting the specific gravity of the emulsion to obtain polytetrafluoroethylene dispersion with 30% of solid content.
Comparative example 1
The preparation of polytetrafluoroethylene dispersion provided in this comparative example differs from example 1 only in that no modifier perfluorobutyl ethylene was added in step 1) of this comparative example.
Comparative example 2
The preparation method of polytetrafluoroethylene dispersion provided in this comparative example is different from example 1 in that in step 1) of this comparative example, when the reaction vessel is heated to 75 ℃, gaseous monomer tetrafluoroethylene is charged, and the polymerization reaction temperature is controlled to 78-85 ℃.
Comparative example 3
The preparation method of the polytetrafluoroethylene dispersion provided in the present comparative example is different from that of example 1 in that the addition amount of the branched secondary alcohol polyoxyethylene ether as the emulsifier in step 2) of the present comparative example is 1.5% of the dry polytetrafluoroethylene material.
Comparative example 4
The preparation method of the polytetrafluoroethylene dispersion provided in the present comparative example is different from that of example 1 in that the addition amount of the branched secondary alcohol polyoxyethylene ether as the emulsifier in step 2) of the present comparative example is 3.5% of the dry polytetrafluoroethylene material.
Comparative example 5
The preparation method of the polytetrafluoroethylene dispersion provided in the comparative example comprises the following steps:
1) A50L stainless steel high-pressure reaction kettle is cleaned, 32L of 16MΩ high-purity deionized water, 8g of dispersing agent fluorine-containing polyether ammonium carboxylate and 2kg of stabilizer paraffin are added, the kettle is closed, the kettle is evacuated and replaced by nitrogen, and then the oxygen content is analyzed, and the kettle is qualified when the oxygen content is less than or equal to 30 ppm. The reaction kettle is heated to 72 ℃, gaseous monomer tetrafluoroethylene is added until the pressure in the kettle is 2.5MPa, and 2L of aqueous solution containing 10g (pure) of succinic peroxide as an initiator is added through a metering pump. The pressure in the reactor is maintained at 2.5MPa and the temperature is 74+/-1 ℃. The initiator may be appropriately added according to the polymerization rate, and the number of additions depends on the reaction rate. When the feeding amount of the tetrafluoroethylene reaches 3Kg, 1L of aqueous solution containing 42g of residual dispersing agent fluorine-containing polyether ammonium carboxylate is continuously and uniformly added into the polymerization system, and when the feeding amount of the tetrafluoroethylene reaches 8Kg, the adding is completed. When the feeding amount of the tetrafluoroethylene reaches 20Kg, the reaction is finished, the gas phase monomer is recovered, the temperature is reduced, the discharging is carried out, and paraffin is separated, so that polytetrafluoroethylene polymerization solution with the solid content of about 34% is obtained.
2) Adding branched secondary alcohol polyoxyethylene ether serving as an emulsifier and accounting for 2.5% of the dry polytetrafluoroethylene material into the obtained polytetrafluoroethylene polymerization solution, stirring at a low speed of 10r/min in a dosing tank for 1.5-2 hours, adding a pH regulator tetramethylammonium hydroxide aqueous solution to adjust the pH value to about 8 (measured by pH test paper), and adjusting the specific gravity of the emulsion to obtain polytetrafluoroethylene dispersion with 30% of solid content.
Comparative example 6
The preparation method of polytetrafluoroethylene dispersion provided in this comparative example is different from example 1 in that step 2) of this comparative example: adding branched secondary alcohol polyoxyethylene ether serving as an emulsifier and accounting for 6% of the dry polytetrafluoroethylene material into the obtained polytetrafluoroethylene polymerization solution, carrying out vacuum concentration, adding a pH regulator, namely tetramethylammonium hydroxide aqueous solution, to adjust the pH value to about 8 (measured by pH test paper), and adjusting the specific gravity of the emulsion to obtain polytetrafluoroethylene concentrated dispersion with the solid content of 60%.
Test case
The polytetrafluoroethylene dispersions prepared in examples 1-2 and comparative examples 1-6 and polytetrafluoroethylene copper-clad laminate prepared from the polytetrafluoroethylene dispersions were tested for performance, and the results are shown in Table 1.
Test standard:
particle size-GB/T19077.1-2008;
solids content-ASTM D4441-2004
Emulsifier content-ASTM D4441-2004;
zeta potential-ISO 13099-3;
SSG-ASTM D4441-2004；
dielectric loss factor-GB/T12636-90;
the preparation method of the polytetrafluoroethylene copper-clad plate comprises the following steps: 1. uniformly mixing raw material components such as polytetrafluoroethylene emulsion, ceramic powder, short glass fiber and the like by a wet method, flocculating, drying the materials, and adding a lubricant for curing; 2. extruding, calendaring to obtain a green sheet, and drying; 3. and covering copper foil on two sides of the green substrate, sintering, maintaining the pressure, and cooling to room temperature to obtain the polytetrafluoroethylene copper-clad plate.
TABLE 1 polytetrafluoroethylene dispersion and measurement of product properties
While the invention has been described in detail in the foregoing general description, embodiments and experiments, it will be apparent to those skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.
Claims (17)
1. The preparation method of the polytetrafluoroethylene dispersion for the copper-clad plate is characterized by comprising the following steps of:
1) Adding a modifier, a tetrafluoroethylene monomer and an initiator into a reaction kettle containing deionized water, a dispersing agent and a stabilizing agent, wherein the content of internal oxygen is not more than 30ppm, controlling the temperature of polymerization reaction to be 74+/-1 ℃ and the pressure to be 2.2-2.8Mpa, and obtaining polytetrafluoroethylene polymerization solution with the solid content of 29-31%;
2) Adding an emulsifier and a pH regulator into the polytetrafluoroethylene polymerization solution to obtain polytetrafluoroethylene dispersion;
the modifier is perfluorobutyl ethylene, and the dosage of the modifier is 0.003-0.011% of the mass of deionized water;
the emulsifier is branched secondary alcohol polyoxyethylene ether, and the dosage of the emulsifier is 2-3% of the dry polytetrafluoroethylene material.
2. The method according to claim 1, wherein the modifier is used in an amount of 0.003-0.0095% by mass of deionized water.
3. The preparation method according to claim 1 or 2, wherein the amount of the emulsifier is 2.3-2.7% of the dry polytetrafluoroethylene.
4. The method of claim 1, wherein the deionized water is present in an amount of 50-70% of the reactor volume.
5. The method according to claim 4, wherein the deionized water is used in an amount of 60-70% of the volume of the reaction vessel.
6. The preparation method according to claim 1, wherein the tetrafluoroethylene monomer is added in the form of a gaseous tetrafluoroethylene monomer, and the addition amount of the tetrafluoroethylene monomer is 40-60% of the mass of deionized water.
7. The preparation method according to claim 6, wherein the input amount of the tetrafluoroethylene monomer is 45-57% of the mass of deionized water.
8. The method of preparation of claim 1, wherein the dispersant is an ammonium perfluorooctanoate substitute; the consumption of the dispersing agent is 0.01-0.15% of the mass of the deionized water.
9. The method of preparation of claim 8, wherein the dispersant is one or more of perfluoro or fluorine-containing polyether carboxylate, perfluoro or fluorine-containing alkyl ammonium carboxylate or salt thereof, perfluoro or fluorine-containing alkyl ammonium sulfonate or salt thereof;
the consumption of the dispersing agent is 0.05-0.1% of the mass of the deionized water.
10. The method of claim 9, wherein the dispersant is a perfluoro or fluoropolyether carboxylate.
11. The preparation method according to claim 1, wherein the stabilizer is solid paraffin or saturated hydrocarbon with carbon number more than or equal to 12;
the dosage of the stabilizer is 1.0-8.0% of the mass of the deionized water.
12. The method of claim 11, wherein the stabilizer is paraffin wax, and the melting point of the paraffin wax is 56-58 ℃; the dosage of the stabilizer is 3.0-6.0% of the mass of the deionized water.
13. The method of claim 1, wherein the initiator is an inorganic initiator and/or an organic initiator; the inorganic initiator is persulfate of alkali metal, and the organic initiator is peroxide;
the initiator is used in an amount of 0.01-0.07% of the mass of deionized water.
14. The method according to claim 13, wherein the inorganic initiator is one or both of ammonium persulfate and potassium persulfate; the organic initiator is one or two of benzoyl peroxide and succinic acid peroxide; the initiator is used in an amount of 0.02-0.05% of the mass of deionized water.
15. The method according to claim 1, wherein the pH adjuster is one or more selected from the group consisting of sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, and aqueous ammonia.
16. The method of claim 15, wherein the pH adjustment is tetramethylammonium hydroxide.
17. Polytetrafluoroethylene dispersion for copper-clad plates prepared by the method of any one of claims 1 to 16.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0111342A1 (en) * | 1982-12-13 | 1984-06-20 | E.I. Du Pont De Nemours And Company | Non-melt-fabricable granular modified terafluoroethylene polymer |
| CN110845653A (en) * | 2018-08-20 | 2020-02-28 | 中昊晨光化工研究院有限公司 | Polytetrafluoroethylene dispersion concentrate and preparation method thereof |
| CN111285954A (en) * | 2020-03-16 | 2020-06-16 | 山东东岳高分子材料有限公司 | Preparation method of high molecular weight modified polytetrafluoroethylene dispersion resin and dispersion concentrated solution |
| CN112552530A (en) * | 2019-09-26 | 2021-03-26 | 中昊晨光化工研究院有限公司 | Polytetrafluoroethylene concentrated dispersion and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0111342A1 (en) * | 1982-12-13 | 1984-06-20 | E.I. Du Pont De Nemours And Company | Non-melt-fabricable granular modified terafluoroethylene polymer |
| CN110845653A (en) * | 2018-08-20 | 2020-02-28 | 中昊晨光化工研究院有限公司 | Polytetrafluoroethylene dispersion concentrate and preparation method thereof |
| CN112552530A (en) * | 2019-09-26 | 2021-03-26 | 中昊晨光化工研究院有限公司 | Polytetrafluoroethylene concentrated dispersion and preparation method thereof |
| CN111285954A (en) * | 2020-03-16 | 2020-06-16 | 山东东岳高分子材料有限公司 | Preparation method of high molecular weight modified polytetrafluoroethylene dispersion resin and dispersion concentrated solution |
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