CN102532496B - Fluorine-containing bisphenol aromatic polyester and preparation method thereof - Google Patents
Fluorine-containing bisphenol aromatic polyester and preparation method thereof Download PDFInfo
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- CN102532496B CN102532496B CN201110425267.1A CN201110425267A CN102532496B CN 102532496 B CN102532496 B CN 102532496B CN 201110425267 A CN201110425267 A CN 201110425267A CN 102532496 B CN102532496 B CN 102532496B
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Abstract
The invention relates to fluorine-containing bisphenol aromatic polyester and a preparation method thereof. The fluorine-containing bisphenol aromatic polyester comprises a fluorine-containing aromatic bisphenol structural unit and an aromatic dibenzoyl structural unit, and is prepared via fusion and polycondensation of a fluorine-containing aromatic bisphenol compound and an aromatic phthalate acid compound. The aromatic polyester is suitable for large-scale industrial production. Moreover, the prepared aromatic polyester contains fluorine, and the intrinsic viscosity [Eta]is 0.5-7dl/g. In addition to the advantages of ordinary polyarylate, the aromatic polyester also has excellent heat resistance, aging resistance, a low dielectric constant, low capacitance and other electrical properties. The scope of application of the traditional polyarylate is expanded.
Description
Technical field
The invention belongs to polymeric material field, relate to a kind of fluorine-containing bisphenol aromatic polyester and preparation method thereof, be specially a kind of fluorine-containing bisphenol aromatic polyester that comprises fluorine-containing bis-phenol structural unit and aromatics two formyl structural units and preparation method thereof.
Background technology
Japan You Niqika (Unitika) company takes the lead in adopting mixing dioctyl phthalate and dihydroxyphenyl propane to synthesize a kind of polyarylester (its commodity are called the basic trade mark U-100 of U-Polymer).Due to its remarkable resistance toheat, there is high strength simultaneously, high-modulus, resistance ultraviolet linearity, the plurality of advantages such as creep resistance, increasing people has launched research to it, by from molecular level, its structure being modified to improve its processibility and given better properties, meets the demand of people to functional materials.Domestic patent 200510060698.7 and 200610022133.4 has reported that the different substituting group of introducing synthesizes polyarylester in the bisphenol A-type monomer, makes its melting point depression and gives polyarylester more performance, has expanded the range of application of polyarylester; Champion's Chen (Jiangxi Normal University's Master's thesis, 2009) reported phase transfer method bisphenol synthesis S type polyarylester, with 4,4-dihydroxy diphenylsulphone (BPS) replaces 2, two (4-hydroxy phenyl) propane (dihydroxyphenyl propane) of 2-has obtained the larger polyarylester of intensity by liquid polymerization, has promoted its performance.
On the other hand, because fluoropolymer has ageing-resistant, resistance to chemical attack and low electric capacity, low combustible, the series of advantages such as low-refraction become one of focus of various countries' broad research, although people have prepared a lot of fluorochemicalss and polymkeric substance but the report of fluorine-containing polyarylester is also rare in recent years, domestic patent 200880115258.9 is by letex polymerization and use perfluor ester group-sulfinate to make the prepared fluoropolymer of dispersion agent to comprise the tetrafluoroethylene polymerization unit, but prepared fluorine-containing polyester is performed poor aspect thermomechanical property.Domestic patent 200780030813.3 has been reported the preparation of aliphatics fluoropolymer, the method is made by polymerization in the reaction medium that comprises water and selected low-telogenic hydrofluoroether (HFE) by least one fluorinated monomer, and complex steps and prepared fluoropolymer can not guarantee to have higher molecular weight.In fluorine-containing polyester prepared by domestic patent 200510075827.X, though used fluorine-containing aromatic monomer contain the fatty ether structural unit in polyester backbone and not fluorine-containing be not fluorine-containing aromatic polyester truly, and above method mostly adopts liquid polymerization, the recycled solvent difficulty, easily pollute, be unfavorable for large-scale industrial production.
Summary of the invention
The purpose of this invention is to provide a kind of fluorine-containing bisphenol aromatic polyester and preparation method thereof, the problem that the present invention exists for prior art just puts forward, adopt the melt phase polycondensation can serialization production, do not relate to utilization and the recovery of solvent, production cost is low can be to environment yet, and obtained aromatic polyester is fluorine-containing for the performance that improves traditional polyarylester and expand its range of application condition is provided.
A kind of fluorine-containing bisphenol aromatic polyester of the present invention is characterized in that the unit structure type of described fluorine-containing bisphenol aromatic polyester is:
In formula: X and Y are respectively alkyl, the phenyl of fluorine atom replacement or the aralkyl that fluorine atom replaces that fluorine atom replaces;
Ar and Dr are respectively following structure
R wherein
1to R
6for hydrogen atom, fluorine atom, phenyl, the carbonatoms alkyl that is 1 to 8 or the carbonatoms aralkyl that is 7 to 12;
Described fluorine-containing bisphenol aromatic polyester limiting viscosity is 0.5～7dl/g.
A kind of fluorine-containing bisphenol aromatic polyester as above, the alkyl that described fluorine replaces refers to:
A kind of fluorine-containing bisphenol aromatic polyester as above, the phenyl that described fluorine replaces refers to:
A kind of fluorine-containing bisphenol aromatic polyester as above, the aralkyl that described fluorine replaces refers to:
The present invention also provides a kind of preparation method of fluorine-containing bisphenol aromatic polyester, comprises the following steps:
(1) acetylize: fluorine-containing aromatic bisphenols type compound and acetylation reagent are added in reactor in 1: 2 in molar ratio～1: 2.8, add catalyzer, return stirring 0.5h～3h, completely reacted solution is poured in frozen water, after Precipitation, throw out is filtered, washing, drying obtains fluorine-containing aromatic bisphenols type acetyl compound;
(2) melt phase polycondensation: described fluorine-containing aromatic bisphenols type acetyl compound and aromatic dicarboxylic acid compound are added in polymeric kettle in molar ratio at 100～110: 100; stir; be filled with nitrogen and add initiator to be warming up to 250 ℃～300 ℃, after reaction 3h～5h, stop inflated with nitrogen; vacuumize; vacuum tightness is 20KPa～60KPa, continues to be warmed up to 300 ℃～350 ℃ reaction 0.5h～8h, emits product; this product is fluorine-containing bisphenol aromatic polyester, and its unit structure type is:
X, Y is respectively alkyl, the phenyl of fluorine atom replacement or the aralkyl that fluorine atom replaces that fluorine atom replaces;
Ar and Dr are respectively following structure
R wherein
1to R
6for hydrogen atom, fluorine atom, phenyl, the carbonatoms alkyl that is 1 to 8 or the carbonatoms aralkyl that is 7 to 12;
Wherein, the combination that described fluorine-containing aromatic bisphenols type compound is a kind of in compound shown below or any two kinds:
The combination that described aromatic dicarboxylic acid compound is a kind of in compound shown below or any two kinds:
The preparation method of a kind of fluorine-containing bisphenol aromatic polyester as above, described acetylation reagent is diacetyl oxide or Acetyl Chloride 98Min.;
The preparation method of a kind of fluorine-containing bisphenol aromatic polyester as above, described catalyzer is the vitriol oil or p-methyl benzenesulfonic acid, consumption is 0.1%～5% of described fluorine-containing aromatic bisphenols type compound and acetylation reagent total mass;
The preparation method of a kind of fluorine-containing bisphenol aromatic polyester as above, described initiator is zinc acetate or Potassium ethanoate, consumption is 0.1%～5% of described fluorine-containing aromatic bisphenols type acetyl compound and aromatic dicarboxylic acid compound total mass.
Beneficial effect:
The invention provides a kind of fluorine-containing bisphenol aromatic polyester and preparation method thereof.Adopt melt phase polycondensation, simple to operate, do not produce the three wastes, be suitable for large-scale industrial production.
The full aromatic(based)polymer molecular weight made is high and contain fluorine atom; strong electronegativity due to fluorine; high C-F bond energy and the polyarylester that the shielding protection effect of carbochain makes to synthesize is also had except the performance of the traditional polyarylester of further lifting remarkable heat-resisting, ageing-resistant, resistance to chemical attack and low electric capacity; low combustible; the performances such as low-refraction, also have some special electric property, as low-k simultaneously; the advantages such as high-insulativity, expanded range of application.
Embodiment
Below in conjunction with embodiment, further set forth the present invention.Should be understood that these embodiment only are not used in and limit the scope of the invention for the present invention is described.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
A kind of fluorine-containing bisphenol aromatic polyester of the present invention, its unit structure type is:
In formula: X and Y are respectively alkyl, the phenyl of fluorine atom replacement or the aralkyl that fluorine atom replaces that fluorine atom replaces;
Ar and Dr are respectively following structure
R wherein
1to R
6for hydrogen atom, fluorine atom, phenyl, the carbonatoms alkyl that is 1 to 8 or the carbonatoms aralkyl that is 7 to 12;
Described fluorine-containing bisphenol aromatic polyester limiting viscosity is 0.5～7dl/g.
The alkyl that described fluorine replaces refers to:
The phenyl that fluorine replaces refers to:
The aralkyl that fluorine replaces refers to:
Embodiment 1
By hexafluoro bisphenol-a and diacetyl oxide, within 1: 2 in molar ratio, add in three mouthfuls of reactors, drip the catalyzer vitriol oil, consumption is 0.1% of hexafluoro bisphenol-a and diacetyl oxide total mass, return stirring 0.5h, completely reacted solution is poured in frozen water, after Precipitation, the mixture of precipitation and frozen water is carried out to suction filtration, the solid obtained is washed till to neutrality with deionized water, 60 ℃ of dry 24h in vacuum drying oven, obtain 2,2-bis-(4-acetoxyl group phenyl) HFC-236fa.
By 2,2-bis-(4-acetoxyl group phenyl) HFC-236fa, terephthalic acid and m-phthalic acid are to add in polymeric kettle at 1: 0.9: 0.1 in molar ratio, add the initiator zinc acetate, consumption is 0.1% of reactant total mass, stirs and be filled with nitrogen, be warming up to 250 ℃, react after 3 hours, stop inflated with nitrogen, vacuumize, vacuum tightness is 20KPa, be warming up to 300 ℃ of reactions after 1.5 hours, emit product, this product is fluorine-containing bisphenol aromatic polyester.
Embodiment 2
By two (4-hydroxy phenyl) methylene fluoride and Acetyl Chloride 98Min., within 1: 2.1 in molar ratio, add in three mouthfuls of reactors, add the catalyzer p-methyl benzenesulfonic acid, consumption is 0.5% of two (4-hydroxy phenyl) methylene fluoride and Acetyl Chloride 98Min. total mass, return stirring 2h, completely reacted solution is poured in frozen water, after Precipitation, the mixture of precipitation and frozen water is carried out to suction filtration, the solid obtained is washed till to neutrality with deionized water, 60 ℃ of dry 24h in vacuum drying oven, obtain two (4-acetoxyl group phenyl) methylene fluoride.
By two (4-acetoxyl group phenyl) methylene fluoride, terephthalic acid and m-phthalic acid are to add at 1: 0.8: 0.2 in polymeric kettle in molar ratio, add the initiator zinc acetate, consumption is 0.2% of reactant total mass, stir and be filled with nitrogen, be warming up to 260 ℃, after reacting 3 hours, stop inflated with nitrogen, vacuumize, vacuum tightness is 25KPa, is warming up to 310 ℃ of reactions after 1 hour, emit product, this product is fluorine-containing bisphenol aromatic polyester.
Embodiment 3
By 2, 2-bis-(4-hydroxy phenyl)-1, 1, 1-Halothane and Acetyl Chloride 98Min., within 1: 2.1 in molar ratio, add in three mouthfuls of reactors, add the catalyzer p-methyl benzenesulfonic acid, consumption is 2, 2-bis-(4-hydroxy phenyl)-1, 1, 1% of 1-Halothane and Acetyl Chloride 98Min. total mass, return stirring 1h, completely reacted solution is poured in frozen water, after Precipitation, the mixture of precipitation and frozen water is carried out to suction filtration, the solid obtained is washed till to neutrality with deionized water, 60 ℃ of dry 24h in vacuum drying oven, obtain 2, 2-bis-(4-acetoxyl group phenyl)-1, 1, the 1-Halothane.
By 2,2-bis-(4-acetoxyl group phenyl)-1,1,1-Halothane and terephthalic acid are to add at 1.1: 1 in polymeric kettle in molar ratio, add the initiator zinc acetate, and consumption is 0.5% of reactant total mass, stir and be filled with nitrogen, be warming up to 260 ℃, after reacting 3.5 hours, stop inflated with nitrogen, vacuumize, vacuum tightness is 25KPa, is warming up to 310 ℃ of reactions after 0.5 hour, emit product, this product is fluorine-containing bisphenol aromatic polyester.
Embodiment 4
By 2,2-bis-(4-hydroxy phenyl) Octafluorobutane and diacetyl oxide, within 1: 2.2 in molar ratio, add in three mouthfuls of reactors, add the catalyzer vitriol oil, consumption is 2,0.8% of 2-bis-(4-hydroxy phenyl) Octafluorobutane and diacetyl oxide total mass, return stirring 1h, completely reacted solution is poured in frozen water, after Precipitation, the mixture of precipitation and frozen water is carried out to suction filtration, the solid obtained is washed till to neutrality with deionized water, 60 ℃ of dry 24h in vacuum drying oven, obtain 2,2-bis-(4-acetoxyl group phenyl) Octafluorobutane.
Be to add at 1.1: 1 in polymeric kettle in molar ratio by 2,2-bis-(4-acetoxyl group phenyl) Octafluorobutane and m-phthalic acid, add the initiator Potassium ethanoate, consumption is 0.5% of reactant total mass, stir and be filled with nitrogen, be warming up to 265 ℃, after reacting 3 hours, stop inflated with nitrogen, vacuumize, vacuum tightness is 30KPa, is warming up to 320 ℃ of reactions after 3 hours, emit product, this product is fluorine-containing bisphenol aromatic polyester.
Embodiment 5
By 1,1-bis-(4-hydroxy phenyl) HFC-236fa and diacetyl oxide, within 1: 2.3 in molar ratio, add in three mouthfuls of reactors, add the catalyzer vitriol oil, consumption is 1,1% of 1-bis-(4-hydroxy phenyl) HFC-236fa and diacetyl oxide total mass, return stirring 1.5h, completely reacted solution is poured in frozen water, after Precipitation, the mixture of precipitation and frozen water is carried out to suction filtration, the solid obtained is washed till to neutrality with deionized water, 60 ℃ of dry 24h in vacuum drying oven, obtain 1,1-bis-(4-acetoxyl group phenyl) HFC-236fa.
By 1,1-bis-(4-acetoxyl group phenyl) HFC-236fa and 4,4 '-biphenyl dicarboxylic acid is to add in polymeric kettle at 1.05: 1 in molar ratio, add the initiator Potassium ethanoate, consumption is 1% of reactant total mass, stirs and be filled with nitrogen, be warming up to 270 ℃, react after 4 hours, stop inflated with nitrogen, vacuumize, vacuum tightness is 30KPa, be warming up to 320 ℃ of reactions after 2 hours, emit product, this product is fluorine-containing bisphenol aromatic polyester.
Embodiment 6
By 1,2-bis-(4-hydroxy phenyl)-1-perfluor ethyl ethane and diacetyl oxide, within 1: 2.5 in molar ratio, add in three mouthfuls of reactors, add the catalyzer p-methyl benzenesulfonic acid, consumption is 1,1.5% of 2-bis-(4-hydroxy phenyl)-1-perfluor ethyl ethane and diacetyl oxide total mass, return stirring 1.5h, completely reacted solution is poured in frozen water, after Precipitation, the mixture of precipitation and frozen water is carried out to suction filtration, the solid obtained is washed till to neutrality with deionized water, 60 ℃ of dry 24h in vacuum drying oven, obtain 1,2-bis-(4-acetoxyl group phenyl)-1-perfluor ethyl ethane.
By 1,2-bis-(4-acetoxyl group phenyl)-1-perfluor ethyl ethane and 4,4 '-biphenyl dicarboxylic acid is to add in polymeric kettle at 1.1: 1 in molar ratio, add the initiator Potassium ethanoate, consumption is 1% of reactant total mass, stirs and be filled with nitrogen, be warming up to 270 ℃, react after 4 hours, stop inflated with nitrogen, vacuumize, vacuum tightness is 30KPa, be warming up to 320 ℃ of reactions after 4 hours, emit product, this product is fluorine-containing bisphenol aromatic polyester.
Embodiment 7
By 2, 2-bis-(4-hydroxy phenyl)-1, 1, 1-trifluoro propane and Acetyl Chloride 98Min., within 1: 2.3 in molar ratio, add in three mouthfuls of reactors, add the catalyzer p-methyl benzenesulfonic acid, consumption is 2, 2-bis-(4-hydroxy phenyl)-1, 1, 2% of 1-trifluoro propane and Acetyl Chloride 98Min. total mass, return stirring 2h, completely reacted solution is poured in frozen water, after Precipitation, the mixture of precipitation and frozen water is carried out to suction filtration, the solid obtained is washed till to neutrality with deionized water, 60 ℃ of dry 24h in vacuum drying oven, obtain 2, 2-bis-(4-acetoxyl group phenyl)-1, 1, 1-trifluoro propane.
By 2,2-bis-(4-acetoxyl group phenyl)-1,1,1-trifluoro propane and NDA are to add at 1: 1 in polymeric kettle in molar ratio, add the initiator zinc acetate, consumption is 0.5% of reactant total mass, stirs and be filled with nitrogen, is warming up to 270 ℃, react after 4 hours, stop inflated with nitrogen, vacuumize, vacuum tightness is 35KPa, be warming up to 320 ℃ of reactions after 3 hours, emit product, this product is fluorine-containing bisphenol aromatic polyester.
Embodiment 8
By 4, 4-bis-(4-hydroxy phenyl)-1, 1, 1, 2, 3, 3-hexafluoro pentane and diacetyl oxide, within 1: 2.5 in molar ratio, add in three mouthfuls of reactors, add the catalyzer p-methyl benzenesulfonic acid, consumption is 4, 4-bis-(4-hydroxy phenyl)-1, 1, 1, 2, 3, 2% of 3-hexafluoro pentane and diacetyl oxide total mass, return stirring 2h, completely reacted solution is poured in frozen water, after Precipitation, the mixture of precipitation and frozen water is carried out to suction filtration, the solid obtained is washed till to neutrality with deionized water, 60 ℃ of dry 24h in vacuum drying oven, obtain 4, 4-bis-(4-acetoxyl group phenyl)-1, 1, 1, 2, 3, 3-hexafluoro pentane.
By 4,4-bis-(4-acetoxyl group phenyl)-1,1,1,2,3,3-hexafluoro pentane, terephthalic acid and m-phthalic acid are to add at 1.01: 0.5: 0.5 in polymeric kettle in molar ratio, add the initiator zinc acetate, and consumption is 1% of reactant total mass, stir and be filled with nitrogen, be warming up to 270 ℃, after reacting 5 hours, stop inflated with nitrogen, vacuumize, vacuum tightness is 35KPa, be warming up to 320 ℃ of reactions after 4 hours, emit product, this product is fluorine-containing bisphenol aromatic polyester.
Embodiment 9
By 1,4-bis-(4-hydroxy phenyl)-2-fluorobenzene and Acetyl Chloride 98Min., within 1: 2.4 in molar ratio, add in three mouthfuls of reactors, add the catalyzer p-methyl benzenesulfonic acid, consumption is 1,4% of 4-bis-(4-hydroxy phenyl)-2-fluorobenzene and Acetyl Chloride 98Min. total mass, return stirring 2.5h, completely reacted solution is poured in frozen water, after Precipitation, the mixture of precipitation and frozen water is carried out to suction filtration, the solid obtained is washed till to neutrality with deionized water, 60 ℃ of dry 24h in vacuum drying oven, obtain Isosorbide-5-Nitrae-bis-(4-acetoxyl group phenyl)-2-fluorobenzene.
By Isosorbide-5-Nitrae-bis-(4-acetoxyl group phenyl)-2-fluorobenzene, 4,4 '-biphenyl dicarboxylic acid and m-phthalic acid are to add at 1.02: 0.7: 0.3 in polymeric kettle in molar ratio, add the initiator Potassium ethanoate, and consumption is 1% of reactant total mass, stir and be filled with nitrogen, be warming up to 270 ℃, after reacting 4 hours, stop inflated with nitrogen, vacuumize, vacuum tightness is 35KPa, is warming up to 320 ℃ of reactions after 2 hours, emit product, this product is fluorine-containing bisphenol aromatic polyester.
Embodiment 10
By 1,4-bis-(4-hydroxy phenyl)-2,5-difluorobenzene and diacetyl oxide, within 1: 2.5 in molar ratio, add in three mouthfuls of reactors, add the catalyzer vitriol oil, consumption is Isosorbide-5-Nitrae-bis-(4-hydroxy phenyl)-2,1.5% of 5-difluorobenzene and diacetyl oxide total mass, return stirring 2h, pour completely reacted solution in frozen water into, after Precipitation, the mixture of precipitation and frozen water is carried out to suction filtration, the solid obtained is washed till to neutrality with deionized water, and in vacuum drying oven, 60 ℃ of dry 24h, obtain 1,4-bis-(4-acetoxyl group phenyl)-2, the 5-difluorobenzene.
By Isosorbide-5-Nitrae-bis-(4-acetoxyl group phenyl)-2,5-difluorobenzene, NDA and m-phthalic acid are to add at 1.1: 0.9: 0.1 in polymeric kettle in molar ratio, add the initiator zinc acetate, consumption is 2% of reactant total mass, stirs and be filled with nitrogen, is warming up to 275 ℃, react after 4.5 hours, stop inflated with nitrogen, vacuumize, vacuum tightness is 35KPa, be warming up to 325 ℃ of reactions after 4 hours, emit product, this product is fluorine-containing bisphenol aromatic polyester.
Embodiment 11
By two (4-hydroxy phenyls)-(4-fluorophenyl) methane and diacetyl oxide, within 1: 2.5 in molar ratio, add in three mouthfuls of reactors, add the catalyzer vitriol oil, consumption is 1% of two (4-hydroxy phenyls)-(4-fluorophenyl) methane and diacetyl oxide total mass, return stirring 2.5h, completely reacted solution is poured in frozen water, after Precipitation, the mixture of precipitation and frozen water is carried out to suction filtration, the solid obtained is washed till to neutrality with deionized water, 60 ℃ of dry 24h in vacuum drying oven, obtain two (4-acetoxyl group phenyl)-(4-fluorophenyl) methane.
By two (4-acetoxyl group phenyl)-(4-fluorophenyl) methane, 4,4 '-biphenyl dicarboxylic acid and terephthalic acid are to add in polymeric kettle at 1.05: 0.9: 0.1 in molar ratio, add the initiator zinc acetate, consumption is 2.5% of reactant total mass, stirs and be filled with nitrogen, be warming up to 275 ℃, react after 4 hours, stop inflated with nitrogen, vacuumize, vacuum tightness is 40KPa, be warming up to 325 ℃ of reactions after 3 hours, emit product, this product is fluorine-containing bisphenol aromatic polyester.
Embodiment 12
By 2,2-bis-(4-hydroxy phenyl)-2-phenyl trifluoromethanesulfonate ethane and Acetyl Chloride 98Min., within 1: 2.6 in molar ratio, add in three mouthfuls of reactors, add the catalyzer p-methyl benzenesulfonic acid, consumption is 2,2.5% of 2-bis-(4-hydroxy phenyl)-2-phenyl trifluoromethanesulfonate ethane and Acetyl Chloride 98Min. total mass, return stirring 3h, completely reacted solution is poured in frozen water, after Precipitation, the mixture of precipitation and frozen water is carried out to suction filtration, the solid obtained is washed till to neutrality with deionized water, 60 ℃ of dry 24h in vacuum drying oven, obtain 2,2-bis-(4-acetoxyl group phenyl)-2-phenyl trifluoromethanesulfonate ethane.
By 2,2-bis-(4-acetoxyl group phenyl)-2-phenyl trifluoromethanesulfonate ethane, 4,4 '-biphenyl dicarboxylic acid and NDA are to add at 1.08: 0.8: 0.2 in polymeric kettle in molar ratio, add the initiator zinc acetate, consumption is 1.5% of reactant total mass, stirs and be filled with nitrogen, is warming up to 285 ℃, react after 5 hours, stop inflated with nitrogen, vacuumize, vacuum tightness is 45KPa, be warming up to 335 ℃ of reactions after 3 hours, emit product, this product is fluorine-containing bisphenol aromatic polyester.
Embodiment 13
By two (4-hydroxy phenyls)-(4-trifluoromethyl) methane and Acetyl Chloride 98Min., within 1: 2.7 in molar ratio, add in three mouthfuls of reactors, add the catalyzer p-methyl benzenesulfonic acid, consumption is 3% of two (4-hydroxy phenyls)-(4-trifluoromethyl) methane and Acetyl Chloride 98Min. total mass, return stirring 3h, completely reacted solution is poured in frozen water, after Precipitation, the mixture of precipitation and frozen water is carried out to suction filtration, the solid obtained is washed till to neutrality with deionized water, 60 ℃ of dry 24h in vacuum drying oven, obtain two (4-acetoxyl group phenyl)-(4-trifluoromethyl) methane.
By two (4-acetoxyl group phenyl)-(4-trifluoromethyl) methane and 4,4 '-biphenyl dicarboxylic acid is to add at 1.1: 1 in polymeric kettle in molar ratio, adds the initiator Potassium ethanoate, consumption is 2% of reactant total mass, stir and be filled with nitrogen, be warming up to 285 ℃, after reacting 5 hours, stop inflated with nitrogen, vacuumize, vacuum tightness is 45KPa, is warming up to 335 ℃ of reactions after 5 hours, emit product, this product is fluorine-containing bisphenol aromatic polyester.
Embodiment 14
By 2, 2-bis-(4-hydroxy phenyl)-2-(3-trifluoromethyl) Halothane and diacetyl oxide, within 1: 2.6 in molar ratio, add in three mouthfuls of reactors, add the catalyzer p-methyl benzenesulfonic acid, consumption is 2, 1% of 2-bis-(4-hydroxy phenyl)-2-(3-trifluoromethyl) Halothane and diacetyl oxide total mass, return stirring 3h, completely reacted solution is poured in frozen water, after Precipitation, the mixture of precipitation and frozen water is carried out to suction filtration, the solid obtained is washed till to neutrality with deionized water, 60 ℃ of dry 24h in vacuum drying oven, obtain 2, 2-bis-(4-acetoxyl group phenyl)-2-(3-trifluoromethyl) Halothane.
By 2,2-bis-(4-acetoxyl group phenyl)-2-(3-trifluoromethyl) Halothane, terephthalic acid and 2, the 6-naphthalic acid is to add at 1.08: 0.6: 0.4 in polymeric kettle in molar ratio, adds the initiator zinc acetate, and consumption is 3% of reactant total mass, stir and be filled with nitrogen, be warming up to 290 ℃, after reacting 5 hours, stop inflated with nitrogen, vacuumize, vacuum tightness is 45KPa, is warming up to 335 ℃ of reactions after 5 hours, emit product, this product is fluorine-containing bisphenol aromatic polyester.
Embodiment 15
By 4,4-bis-(4-hydroxy phenyl)-4-phenyl-seven fluorine butane and Acetyl Chloride 98Min., within 1: 2.8 in molar ratio, add in three mouthfuls of reactors, add the catalyzer vitriol oil, consumption is 4,0.5% of 4-bis-(4-hydroxy phenyl)-4-phenyl-seven fluorine butane and Acetyl Chloride 98Min. total mass, return stirring 3h, completely reacted solution is poured in frozen water, after Precipitation, the mixture of precipitation and frozen water is carried out to suction filtration, the solid obtained is washed till to neutrality with deionized water, 60 ℃ of dry 24h in vacuum drying oven, obtain 4,4-bis-(4-acetoxyl group phenyl)-4-phenyl-seven fluorine butane.
By 4,4-bis-(4-acetoxyl group phenyl)-4-phenyl-seven fluorine butane, m-phthalic acid and 2, the 6-naphthalic acid is to add at 1: 0.6: 0.4 in polymeric kettle in molar ratio, adds the initiator zinc acetate, and consumption is 3% of reactant total mass, stir and be filled with nitrogen, be warming up to 295 ℃, after reacting 5 hours, stop inflated with nitrogen, vacuumize, vacuum tightness is 50KPa, is warming up to 350 ℃ of reactions after 6 hours, emit product, this product is fluorine-containing bisphenol aromatic polyester.
The acetylize of the fluorine-containing bisphenol type compound in following examples 16～25 is the same with above-described embodiment method, and the molar ratio of fluorine-containing bisphenol type compound and acetylation reagent is 1: 2～1: 2.8, and return time is at 0.5～3h.
Embodiment 16
By 2,2-bis-(4-acetoxyl group phenyl) HFC-236fa, 4,4-bis-(4-acetoxyl group phenyl)-4-phenyl-seven fluorine butane, m-phthalic acid and NDA are 0.2: 0.8: 0.6 in molar ratio: 0.4 adds in polymeric kettle, adds the initiator zinc acetate, consumption is 0.5% of reactant total mass, stir and be filled with nitrogen, be warming up to 290 ℃, after reacting 3 hours, stop inflated with nitrogen, vacuumize, vacuum tightness is 50KPa, is warming up to 310 ℃ of reactions after 8 hours, emit product, this product is fluorine-containing bisphenol aromatic polyester.
Embodiment 17
By two (4-acetoxyl group phenyl) methylene fluoride, 2,2-bis-(4-acetoxyl group phenyl)-2-(3-trifluoromethyl) Halothane and m-phthalic acid are to add in polymeric kettle at 0.4: 0.7: 1 in molar ratio, add the initiator zinc acetate, consumption is 1% of reactant total mass, stir and be filled with nitrogen, be warming up to 295 ℃, react after 4 hours, stop inflated with nitrogen, vacuumize, vacuum tightness is 55KPa, be warming up to 340 ℃ of reactions after 4 hours, emit product, this product is fluorine-containing bisphenol aromatic polyester.
Embodiment 18
By 2,2-bis-(4-acetoxyl group phenyl)-1,1, the 1-Halothane, two (4-acetoxyl group phenyl)-(4-trifluoromethyl) methane and NDA are to add at 0.5: 0.5: 1 in polymeric kettle in molar ratio, add the initiator zinc acetate, consumption is 3% of reactant total mass, stir and be filled with nitrogen, be warming up to 275 ℃, after reacting 4 hours, stop inflated with nitrogen, vacuumize, vacuum tightness is 60KPa, is warming up to 340 ℃ of reactions after 6 hours, emit product, this product is fluorine-containing bisphenol aromatic polyester.
Embodiment 19
By 2,2-bis-(4-acetoxyl group phenyl) Octafluorobutane, 2,2-bis-(4-acetoxyl group phenyl)-2-phenyl trifluoromethanesulfonate ethane, m-phthalic acid and 4,4 '-biphenyl dicarboxylic acid is 0.2: 0.8: 0.6 in molar ratio: 0.4 adds in polymeric kettle, adds the initiator zinc acetate, consumption is 0.5% of reactant total mass, stir and be filled with nitrogen, be warming up to 290 ℃, after reacting 3 hours, stop inflated with nitrogen, vacuumize, vacuum tightness is 50KPa, is warming up to 320 ℃ of reactions after 7 hours, emit product, this product is fluorine-containing bisphenol aromatic polyester.
Embodiment 20
By 1,1-bis-(4-acetoxyl group phenyl) HFC-236fa, 1,4-bis-(4-acetoxyl group phenyl)-2,5-difluorobenzene, terephthalic acid and 4,4 '-biphenyl dicarboxylic acid is 0.3: 0.8: 0.5 in molar ratio: 0.5 adds in polymeric kettle, add the initiator Potassium ethanoate, consumption is 2% of reactant total mass, stirs and be filled with nitrogen, be warming up to 300 ℃, react after 2 hours, stop inflated with nitrogen, vacuumize, vacuum tightness is 55KPa, be warming up to 340 ℃ of reactions after 3 hours, emit product, this product is fluorine-containing bisphenol aromatic polyester.
Embodiment 21
By 1,2-bis-(4-acetoxyl group phenyl)-1-perfluor ethyl ethane, 2,2-bis-(4-acetoxyl group phenyl)-2-phenyl trifluoromethanesulfonate ethane, terephthalic acid and 4,4 '-biphenyl dicarboxylic acid is 0.5: 0.5: 0.5 in molar ratio: 0.5 adds in polymeric kettle, adds the initiator Potassium ethanoate, consumption is 4% of reactant total mass, stir and be filled with nitrogen, be warming up to 300 ℃, after reacting 5 hours, stop inflated with nitrogen, vacuumize, vacuum tightness is 55KPa, is warming up to 350 ℃ of reactions after 2 hours, emit product, this product is fluorine-containing bisphenol aromatic polyester.
Embodiment 22
By 2,2-bis-(4-acetoxyl group phenyl)-1,1,1-trifluoro propane, two (4-acetoxyl group phenyl)-(4-fluorophenyl) methane, 2,6-naphthalic acid and m-phthalic acid are 0.5: 0.5: 0.5 in molar ratio: 0.5 adds in polymeric kettle, add the initiator Potassium ethanoate, consumption is 3% of reactant total mass, stirs and be filled with nitrogen, be warming up to 300 ℃, react after 2 hours, stop inflated with nitrogen, vacuumize, vacuum tightness is 60KPa, be warming up to 320 ℃ of reactions after 8 hours, emit product, this product is fluorine-containing bisphenol aromatic polyester.
Embodiment 23
By 4,4-bis-(4-acetoxyl group phenyl)-1,1,1,2,3,3-hexafluoro pentane, Isosorbide-5-Nitrae-bis-(4-acetoxyl group phenyl)-2-fluorobenzene, 2, the 6-naphthalic acid is to add in polymeric kettle at 0.7: 0.3: 1 in molar ratio, add the initiator Potassium ethanoate, consumption is 5% of reactant total mass, stirs and be filled with nitrogen, be warming up to 290 ℃, react after 4 hours, stop inflated with nitrogen, vacuumize, vacuum tightness is 60KPa, be warming up to 350 ℃ of reactions after 5 hours, emit product, this product is fluorine-containing bisphenol aromatic polyester.
Embodiment 24
By 4,4-bis-(4-acetoxyl group phenyl)-1,1,1,2,3,3-hexafluoro pentane, 2,2-bis-(4-acetoxyl group phenyl)-1,1,1-trifluoro propane, 2,6-naphthalic acid and m-phthalic acid are 0.1: 0.9: 0.1 in molar ratio: 0.9 adds in polymeric kettle, add the initiator Potassium ethanoate, consumption is 3% of reactant total mass, stirs and be filled with nitrogen, be warming up to 290 ℃, react after 2 hours, stop inflated with nitrogen, vacuumize, vacuum tightness is 60KPa, be warming up to 350 ℃ of reactions after 7 hours, emit product, this product is fluorine-containing bisphenol aromatic polyester.
Embodiment 25
By 2,2-bis-(4-acetoxyl group phenyl)-2-phenyl trifluoromethanesulfonate ethane, 2,2-bis-(4-acetoxyl group phenyl) Octafluorobutane, 4,4 '-biphenyl dicarboxylic acid and terephthalic acid are 0.8: 0.3: 0.7 in molar ratio: 0.3 adds in polymeric kettle, adds the initiator Potassium ethanoate, consumption is 5% of reactant total mass, stir and be filled with nitrogen, be warming up to 290 ℃, after reacting 2 hours, stop inflated with nitrogen, vacuumize, vacuum tightness is 60KPa, is warming up to 350 ℃ of reactions after 5 hours, emit product, this product is fluorine-containing bisphenol aromatic polyester.
Claims (1)
1. the preparation method of a fluorine-containing bisphenol aromatic polyester is characterized in that comprising the following steps:
(1) acetylize: by fluorine-containing aromatic bisphenols type compound and acetylation reagent in molar ratio 1:2～1:2.8 add in reactor, add catalyzer, return stirring 0.5h～3h, completely reacted solution is poured in frozen water, after Precipitation, throw out is filtered, washing, drying obtains fluorine-containing aromatic bisphenols type acetyl compound;
(2) melt phase polycondensation: by described fluorine-containing aromatic bisphenols type acetyl compound and aromatic dicarboxylic acid compound in molar ratio 100～110:100 add in polymeric kettle; stir; be filled with nitrogen and add initiator to be warming up to 250 ℃～300 ℃, after reaction 3h～5h, stop inflated with nitrogen; vacuumize; vacuum tightness is 20KPa～60KPa, continues to be warmed up to 300 ℃～350 ℃ reaction 0.5h～8h, emits product; this product is fluorine-containing bisphenol aromatic polyester, and its unit structure type is:
In formula, X and Y are respectively alkyl, the phenyl of fluorine atom replacement or the aralkyl that fluorine atom replaces that fluorine atom replaces;
Ar and Dr are respectively following structure
R wherein
1to R
6the aralkyl that the alkyl that to be respectively hydrogen atom, fluorine atom, phenyl, carbonatoms be 1 to 8 or carbonatoms are 7 to 12;
Wherein, the combination that described fluorine-containing aromatic bisphenols type compound is a kind of in compound shown below or any two kinds:
The combination that described aromatic dicarboxylic acid compound is a kind of in compound shown below or any two kinds:
Described acetylation reagent is diacetyl oxide or Acetyl Chloride 98Min.;
Described catalyzer is the vitriol oil or p-methyl benzenesulfonic acid, and consumption is 0.1%～5% of described fluorine-containing aromatic bisphenols type compound and acetylation reagent total mass;
Described initiator is zinc acetate or Potassium ethanoate, and consumption is 0.1%～5% of described fluorine-containing aromatic bisphenols type acetyl compound and aromatic dicarboxylic acid compound total mass.
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| CN114149573A (en) * | 2021-04-21 | 2022-03-08 | 惠生(中国)投资有限公司 | Fluorine-containing liquid crystal copolyester and finished low-dielectric liquid crystal polymer composition |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1526749A (en) * | 2003-09-22 | 2004-09-08 | 吉林大学 | Fluoropolyester and its synthesis and application in preparing array waveguide grating |
| CN101003618A (en) * | 2006-12-25 | 2007-07-25 | 山东东岳神舟新材料有限公司 | Plastic of polyester ketone containing fluorin, and preparation method |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1526749A (en) * | 2003-09-22 | 2004-09-08 | 吉林大学 | Fluoropolyester and its synthesis and application in preparing array waveguide grating |
| CN101003618A (en) * | 2006-12-25 | 2007-07-25 | 山东东岳神舟新材料有限公司 | Plastic of polyester ketone containing fluorin, and preparation method |
Non-Patent Citations (2)
| Title |
|---|
| 六氟双酚A环状聚酯二聚体的开环聚合与表征;郭庆中等;《武汉工程大学学报》;20110731;第33卷(第7期);41-44 * |
| 郭庆中等.六氟双酚A环状聚酯二聚体的开环聚合与表征.《武汉工程大学学报》.2011,第33卷(第7期),41-44. |
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