CN115368507A - Amorphous fluoropolymer, composition containing same, and preparation method and application thereof - Google Patents
Amorphous fluoropolymer, composition containing same, and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides an amorphous fluorine-containing polymer, a composition containing the amorphous fluorine-containing polymer, and a preparation method and application of the amorphous fluorine-containing polymer, and belongs to the technical field of fluorine-containing high polymer materials. The amorphous polymer has a structural unit A based on a perfluoro diene of formula I, a structural unit B based on a perfluoro heterocycloolefin monomer and a structural unit C based on a formula II; content of structural units a, B, C: 18-40 mol% of A structural unit, 38-60mol% of B structural unit and 10-30mol% of C structural unit; wherein formula I is CF 2 =CF（CF 2 ） n OCF=CF 2 Formula II is CF 2 ＝CF(OR f2 ) q ‑(OCF 2 ) m‑ OR f5 . The invention providesThe amorphous fluorine-containing polymer can be dissolved in a fluorine-containing solvent with a wide range, so that the solubility of the amorphous fluorine-containing polymer in the fluorine-containing solvent is improved, and the processing adaptability of the amorphous fluorine-containing polymer is improved.
Description
Technical Field
The invention relates to an amorphous fluorine-containing polymer, a composition containing the same, a preparation method and application thereof, belonging to the technical field of fluorine-containing high polymer materials.
Background
The amorphous fluorine-containing polymer has the characteristics of high transparency, low refractive index, low surface tension and the like, can be dissolved in a specific solvent, and can be prepared into a low refractive index coating used as an optical device through coating, dipping and other modes.
Japanese patent JP13125/1989 discloses a structure of CF 2 ＝CFO(CF 2 ) n CF＝CF 2 (n =1 or 2) to obtain an amorphous polymer having a cyclic structure, which is soluble only in a specific perfluorosolvent, by ring polymerization. U.S. Pat. No. 4,54009 discloses an amorphous polymer obtained by copolymerization of perfluoro-2,2-dimethyl-1,3-heterocyclopentene (PDD for short) with tetrafluoroethylene. The polymer is soluble in a specific solvent and has excellent light transmittance. However, with the increase of the TFE content, tg of the polymer is greatly reduced, crystallinity is generated, transparency is reduced, and solubility in a solvent is reduced; and the reaction monomer is gas and liquid monomer, and the components are difficult to control.
U.S. Pat. No. 5,5502132 uses perfluoroallyl vinyl ether (CF) 2 ＝CFOCF 2 CF＝CF 2 ) Copolymerized with perfluoro-2, 2-dimethyl-1, 3-heterocyclopentene (hereinafter, both abbreviated as PDD), and the composition ratio of these monomers in the copolymer can be freely controlled. The amorphous perfluoropolymer thus obtained has no crystallinity over the entire composition range, and a perfluoropolymer having a glass transition temperature in the range of 70 to 300 ℃ can be obtained while maintaining solvent solubility and transparency. However, the perfluoropolymer obtained in this patent has poor solubility in a part of the solvent.
Patent CN101356230A uses perfluoro allyl vinyl ether or perfluoro butenyl vinyl ether monomer and perfluoro-2, 2-dimethyl-1, 3-heterocyclic pentene and other cyclic structure monomer to copolymerize, to obtain amorphous fluorine-containing polymer soluble in fluorine-containing solvent with boiling point below 70 ℃, and to a certain extent, to expand the selection range of solvent. But the amorphous polymer prepared in this patent has a solubility in fluorine-containing solvents of less than 15g. The inability to prepare high concentration amorphous fluoropolymer solutions limits the range of amorphous polymer applications.
Disclosure of Invention
The invention provides an amorphous fluorine-containing polymer, a composition containing the same, a preparation method and an application thereof, aiming at solving the problem of low solubility of the amorphous polymer in a fluorine-containing solvent in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
an amorphous polymer having structural units A based on a perfluorodiene of formula I, structural units B based on a perfluoroheterocycloalkene monomer and structural units C based on formula II; content of structural units a, B, C: 18-45mol% of A structural unit, 38-60mol% of B structural unit and 10-30mol% of C structural unit;
wherein, formula I: CF (compact flash) 2 =CF（CF 2 ） n OCF=CF 2 (n is 1 or 2),
formula II: CF (compact flash) 2 ＝CF(OR f2 ) q -(OCF 2 ) m -OR f5 Wherein R is f2 Is perfluoroalkyl group with 2-4 carbon atoms, R f5 Is perfluoroalkyl group with 1-4 carbon atoms, q is an integer of 0-3, m is an integer of 0-4, and q + m is an integer of 1-7.
Preferably, R in formula II f2 Is C2 perfluoroalkyl, R f5 Is perfluoroalkyl group having 1 to 2 carbon atoms, and q is an integer of 1 to 3.
Preferably, the content of structural units C is from 23 to 28 mol%.
When n =1 or 2 in the monomer of formula i, the monomer exhibits good ring-forming properties upon polymerization, and the structure is too long or too short to be favorable for ring formation upon polymerization. Further preferably, the monomer of formula I is CF 2 =CF（CF 2 ） 2 OCF=CF 2 。
Preferably, the structural unit B is composed of one or more of perfluoro (2, 2-dimethyl-1, 3-dioxole), perfluoro (4-methyl-1, 3-dioxole), perfluoro (2, 3-dimethyl-1, 3-dioxole), perfluoro (4, 5-dimethyl-2, 2-dioxole), and perfluoro (2, 3-dimethyl-1, 4-dioxin). The monomer in the structural unit B has a cyclic structure, and the existence of the cyclic structure avoids the generation of a crystalline phase, so that an amorphous polymer is formed. The preferred monomer is perfluoro (2, 2-dimethyl-1, 3-dioxole).
Preferably, the monomer of formula ii is selected from one of the following:
CF 2 =CF-OCF 2 CF 2 -(OCF 2 ) 4 -OCF 3 (C9 PEVE for short),
CF 2 ＝CF-OCF 2 CF 2 -(OCF 2 ) 2 -OCF 3 (C7 PEVE for short), CF 2 =CF-(OCF 2 CF 2 ) 2 -OCF 2 CF 3 (EEAVE for short), CF 2 =CF-(OCF 2 CF 2 ) 3 -OCF 2 CF 3 (EEEAVE for short), CF 2 =CF-OCF 2 -OCF 3 、CF 2 ＝CF-OCF 2 -OCF 2 CF 3 、
CF 2 ＝CF-(OCF 2 CF(CF 3 )) 2 - OCF 2 CF 2 CF 3 、CF 2 ＝CF-(OCF 2 ) 2 -OCF 3 。
From the viewpoint of the performance and production efficiency of the amorphous fluoropolymer, one of C9PEVE, C7PEVE, EEAVE and EEEAVE is preferred in formula II.
The structural unit C consisting of the formula II has a long side chain structure, so that the distance between molecular chains can be increased, the van der Waals force of the molecular chains can be reduced, the free volume of the polymer can be increased, and the volume of an amorphous area can be further increased. Thereby increasing the diffusion capacity of the solvent in the amorphous polymer chain, improving the solubility and enlarging the selection range of the solvent.
The existing method for preparing the amorphous polymer mainly introduces a cyclic structure into a main chain, the cyclic structure plays a similar role of internal plasticization, the distance between molecular chains is increased, and Van der Waals force is reduced, so that an amorphous area is formed. The amorphous region has a loose structure, which is beneficial to the entering of a solvent, thereby increasing the solubility in the solvent. We found that the increase in the cyclic structure has a limited effect on solubility, with little effect on solubility beyond the threshold. After the long side chain structure is introduced, a synergistic effect can be formed with the cyclic structure, and the solubility of the amorphous polymer in a solvent can be increased to a greater extent. On the other hand, when a perfluoromonomer having a long side chain structure is used alone, polymerization is difficult due to the side chain volume effect, and it is difficult to form a polymer having a certain molecular weight. And a certain amount of long side chain structure and cyclic structure are introduced into the invention, so that an over-strong steric hindrance effect can be avoided, normal polymerization reaction is not influenced, and the function of increasing solubility can be exerted.
The amorphous fluorine-containing polymer of the invention improves the solubility of the amorphous polymer in a solvent while ensuring the optical performance of the amorphous polymer. The solubility of the polymers of the invention in a particular solvent can be up to 25g to 60g per 100g of solvent. The solvent has carbon number of more than 2 (including 2), fluorine number of 1-20, and boiling point of 30-160 deg.C. The boiling point is lower than 30 ℃, namely the fluorine-containing solvent is boiled at room temperature, and the fluorine-containing solvent has no practical value. The boiling point is higher than 160 ℃, the volatility of the solvent is poor, the solvent volatilization efficiency is low in the using process, and the processing efficiency is low.
Preferably, the solvent is a fluorine-containing solvent with 2-6 carbon atoms and 1-10 fluorine atoms; the fluorine-containing solvent is selected from but not limited to CH 3 CCl 2 F、CF 3 (CF 2 ) 3 CH 2 CH 3 、CF 3 (CF 2 ) 3 OCH 3 、CF 3 (CHF) 2 CF 2 CF 3 、CF 3 CH 2 OCF 2 CHF 2 、CClF 2 CF 2 CHFCl、(CF 3 ) 2 CHOH、CF 3 CF 2 CHCl 2 、CF 3 CF 2 CF 2 CHCl 2 、CClF 2 CF 2 CHClF、CF 3 CF 2 CHFCHFCF 3 、CF 3 CF 2 CF 2 CF 2 CH 2 CH 3 、CF 3 CF 2 CF 2 OCH 3 、CF 3 CF 2 CF 2 OC 2 H 5 Or CF 3 CH 2 OCF 2 CF 2 H.
Said polymer is in CClF 2 CF 2 Solubility in CHClF is 40-55g in CH 3 CCl 2 Solubility in F of 25-45g in CF 3 CH 2 OCF 2 CF 2 The solubility in H is 30-45g.
When the content of the structural unit C is less than 10%, the influence on the polymer structure and solubility is small. When the structure of the structural unit C is improved to more than 10 percent, particularly the content is improved to more than 15 percent, the solubility of the amorphous fluorine-containing polymer in the fluorine-containing solvent is obviously improved. The long-chain branch structure is uniformly distributed among the polymer main chain ring structures, and the ring structures and the long-chain branch structure form a good synergistic effect, so that the van der Waals force among molecular chains is further reduced, the distance among the molecular chains is increased, solvent molecules can easily permeate into the molecular chains, and the solubility is greatly increased. However, when the structural unit C exceeds a certain amount (35%, even 30%), the cyclic structure of the main chain becomes discontinuous, which in turn decreases the light transmittance of the amorphous polymer and impairs the main properties.
The amorphous fluoropolymer according to the present invention is a fluoropolymer having a ring structure in the main chain and a long side chain structure, and the intrinsic viscosity of the fluoropolymer is measured by dissolving the fluoropolymer in perfluoro (2-butyltetrahydrofuran). The intrinsic viscosity of perfluoro (2-butyltetrahydrofuran) at 30 ℃ is in the range of 0.04 to 0.12dL/g. If the intrinsic viscosity is lower than 0.03dL/g, the molecular weight of the fluorine-containing polymer is too low, the strength is low, the fluorine-containing polymer cannot be processed and molded, and the fluorine-containing polymer has no practical value; if the intrinsic viscosity is measured to be higher than 0.12dL/g, the molecular weight of the fluoropolymer becomes too high, and there is a problem that the solubility in the fluorine-containing solvent is poor. A more preferred range of intrinsic viscosity is from 0.05 to 0.10dL/g. The light transmittance of the amorphous fluorine-containing polymer is 95-97%, and the refractive index is 1.3-1.35. The invention improves the solubility of the amorphous polymer, can continuously improve the molecular weight of the amorphous polymer to a certain extent, and is used for preparing coatings with higher molecular weight and strength.
The invention also provides a preparation method of the amorphous fluorine-containing polymer, which comprises the following steps:
mixing water, an emulsifier and a pH regulator, deoxidizing, and adding a mixed monomer; then adding an initiator and a chain transfer agent, carrying out polymerization reaction at 50-120 ℃, and carrying out coagulation or precipitation, drying and end group stabilization treatment on the emulsion after the polymerization reaction to obtain the amorphous fluorine-containing polymer.
Preferably, the reaction temperature is 60 to 100 ℃, more preferably 70 to 90 ℃. The polymerization time is 15-35 hours.
In the invention, the emulsifier is at least one of ammonium perfluorooctanoate and sodium perfluorooctanoate, and the addition amount of the emulsifier is 0.1-2% of the mass of water. The emulsifier can be added directly or dissolved in water and added in the form of aqueous solution.
In the invention, the pH regulator is at least one of disodium hydrogen phosphate and dipotassium hydrogen phosphate, and the addition amount of the pH regulator is 0.01-0.5% of the mass of water. Preferably 0.2 to 0.3%.
Preferably, the chain transfer agent is one or more of dodecanethiol, isopropanol, methanol, ethanol, isopentane, or acetone. The amount of chain transfer agent added is 0.5 to 1.5%, preferably 0.7 to 1.3% of the mass of the mixed monomers.
Preferably, the initiator is one of organic peroxide (such as cumene hydroperoxide, tert-butyl hydroperoxide, benzoyl (BPO), benzoyl peroxide tert-butyl peroxide, diisopropyl peroxydicarbonate and the like) or inorganic peroxide (such as hydrogen peroxide, ammonium persulfate, potassium persulfate and the like), and the addition amount of the initiator is 0.2-1%, preferably 0.4-0.8% of the mass of the mixed monomers.
The mass ratio of the mixed monomer to the water is 0.2-0.3:1. the raw material percentage of the mixed monomer is 20-40 mol% of monomer I, 40-60mol% of perfluoroheterocyclic alkene monomer and 10-35mol% of monomer II.
Preferably, the method for stabilizing the terminal group comprises the following steps: the dried product is treated under a nitrogen-diluted 20% fluorine atmosphere at a pressure of 1.0MPa and a temperature of 150 ℃ for 2 to 8 hours, preferably 3 to 7 hours.
The invention also provides a composition containing the amorphous polymer, which consists of the amorphous polymer and one or more fluorine-containing solvents, wherein the mass percentage of the amorphous polymer in the composition is 0.1-40%; preferably 12 to 35%.
The fluorine-containing solvent may cause damage to the atmospheric ozone layer, and the amorphous polymer composition, due to its higher concentration, reduces the amount of fluorine-containing solvent used during application. And the solubility of the amorphous polymer in the fluorine-containing solvent in the composition is increased, so that various processing modes such as dipping, spraying, spinning, film casting and the like can be met.
The invention also provides the application of the amorphous polymer in optical materials.
The amorphous polymer prepared by the invention is mainly used as an optical material. Amorphous fluoropolymers are excellent optical materials because of their low refractive index and excellent optical clarity. The optical material includes an optical waveguide fiber, an optical lens protective film, an antireflection coating, a semiconductor package passivation film and protective film, a radar coating, and the like.
The amorphous fluoropolymers of the present invention may also be used as elastomers.
The invention has the beneficial effects that:
compared with the prior art, one or more technical schemes provided by the specific embodiment of the invention have at least the following beneficial effects:
1. the invention provides an amorphous fluorine-containing polymer which can be dissolved in a fluorine-containing solvent with a wide range, improves the solubility of the amorphous fluorine-containing polymer in the fluorine-containing solvent and improves the processing adaptability of the amorphous fluorine-containing polymer. The structural unit C has a long side chain structure, so that the distance between molecular chains can be increased, the van der Waals force of the molecular chains is reduced, the free volume of the polymer is increased, and the volume of an amorphous area is further increased. Thereby increasing the diffusion capacity of the solvent in the amorphous polymer chain, improving the solubility and enlarging the selection range of the solvent.
2. The amorphous polymer provided by the invention has higher concentration in the fluorine-containing solvent, so that the using amount of the fluorine-containing solvent is greatly reduced, and the amount of VOCs (volatile organic compounds) in the processing process is reduced; and can meet various processing modes such as dipping, spraying, spinning, film casting and the like, and can be applied to various optical materials.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the practice of the invention.
All the starting materials used in the examples are commercially available, unless otherwise specified.
The tensile strength and elongation test methods for the amorphous fluoropolymers of the present invention are according to ASTM D638, refractive index test method ASTM542, and the reasonable ranges for the amorphous polymers used as optical materials are: 1.29-1.39, and a more preferred range is 1.29-1.35. The light transmittance test method refers to ASTM D1003, and when the material is used as an optical transparent material, the performance requirement of the light transmittance is more than or equal to 90%, and the more excellent performance range is more than or equal to 95%. Solubility, which is the mass of the molten finger dissolved when the solid material reaches saturation in 100g of solvent, was measured at 20 ℃.
The method for testing the light transmittance and the refractive index comprises the following steps: 10g of the fluoropolymer was dissolved in 90g of perfluorotributylamine to obtain a 10% by mass solution. The solution was coated on a quartz plate by spin coating, and the light transmittance at 193nm was measured by an ultraviolet vacuum spectrometer at a coating film thickness of 200 nm. The refractive index of the coating film was measured by Abbe refractometer.
Example 1
An amorphous fluorine-containing polymer and a preparation method thereof, taking a 1000ml polymerization kettle as an example, 400g of deionized water, 15ml of 5wt% ammonium perfluorooctanoate aqueous solution and 1g of disodium hydrogen phosphate are added into a clean polymerization kettle; the nitrogen pressurization and the evacuation and the oxygen removal are repeatedly carried out until the oxygen content is less than 30ppm, and the product is qualified. The composition was then 40mol% CF 2 =CF（CF 2 ） 2 OCF=CF 2 40mol% of perfluoro (2, 2-dimethyl-1, 3-dioxole)) 100g of a 20mol% C9PEVE mixed monomer was charged into a polymerization vessel. The polymerization kettle was heated to 80 ℃ and 5g of a 10% aqueous ammonium persulfate solution was pumped in to initiate the reaction while 1g of the chain transfer agent isopropanol was added. Emulsion polymerization is carried out for 20h at the temperature of 80 ℃, emulsion obtained by the reaction is coagulated by magnesium chloride aqueous solution, washed by deionized water and continuously dried for 20h in a vacuum oven at the temperature of 90 ℃ and the pressure of-0.09 MPa. Then, the terminal stabilization was completed under a 20% fluorine gas atmosphere diluted with nitrogen gas at a pressure of 1.0MPa, a temperature of 150 ℃ and 5 hours. Finally, 95g of a fluoropolymer was obtained.
The polymer was dissolved in perfluoro (2-butyltetrahydrofuran) to give a 10% solution, and the intrinsic viscosity of the fluoropolymer was 0.073dL/g as measured at 30 ℃.
Measurement of fluoropolymer in fluorinated solvent HCF225cb (formula CClF) at 20 deg.C 2 CF 2 CHClF, boiling point 56 ℃), CH 3 CCl 2 F (boiling point 32 ℃ C.), CF 3 CH 2 OCF 2 CF 2 The solubilities of H (boiling point 56 ℃ C.) were 55g,35g and 45g, respectively.
10g of the fluoropolymer was dissolved in 90g of perfluorotributylamine to obtain a 10% solution by mass. The solution was applied to a quartz plate by spin coating, and the transmittance at 193nm was measured by an ultraviolet vacuum spectrometer to determine the light transmittance as a converted coating film thickness of 200nm of 97%. The refractive index of the coating film was measured to be 1.30 with an Abbe refractometer.
Obtained by F19 nuclear magnetic spectrum, based on CF 2 =CF（CF 2 ） 2 OCF=CF 2 Has a structural unit content of 38mol%, a structural unit content of 39mol% based on perfluoro (2, 2-dimethyl-1, 3-dioxole), and a structural unit content of 23mol% based on C9 PEVE.
Example 2
An amorphous fluorine-containing polymer and a preparation method thereof, taking a 1000ml polymerization kettle as an example, 400g of deionized water, 10ml of 5wt% ammonium perfluorooctanoate aqueous solution and 1g of disodium hydrogen phosphate are added into a clean polymerization kettle; the nitrogen pressurization and the evacuation and the oxygen removal are repeatedly carried out until the oxygen content is less than 30ppm, and the product is qualified. Then the composition was determined to be 20mol% 2 =CF（CF 2 ） 2 OCF=CF 2 100g of a mixed monomer containing 45mol% of perfluoro (2, 2-dimethyl-1, 3-dioxole) and 35mol% of C7PEVE was charged into a polymerization reactor. The polymerization kettle was warmed to 70 ℃ and 4g of a 10% aqueous ammonium persulfate solution was pumped in to initiate the reaction while 0.7g of the chain transfer agent isopropanol was added. Emulsion polymerization is carried out for 30h at 70 ℃, emulsion obtained by reaction is coagulated by magnesium chloride aqueous solution, washed by deionized water and continuously dried for 20h in a vacuum oven at 90 ℃ and-0.09 MPa. Then, under a 20% fluorine gas atmosphere diluted with nitrogen gas, under the conditions of a pressure of 1.0MPa and a temperature of 150 ℃, the terminal stabilization process was completed for 6 hours. Finally, 93g of a fluoropolymer was obtained.
This polymer was dissolved in perfluoro (2-butyltetrahydrofuran) to give a 10% solution, and the intrinsic viscosity of the fluoropolymer was 0.09 dL/g as measured at 30 ℃.
Measurement of fluoropolymer in fluorinated solvent HCF225cb (formula CClF) at 20 deg.C 2 CF 2 CHClF, boiling point 56 ℃), CH 3 CCl 2 F (boiling point 32 ℃ C.), CF 3 CH 2 OCF 2 CF 2 The solubilities of H (boiling point: 56 ℃) were 50g,41g and 44g, respectively.
10g of the fluoropolymer was dissolved in 90g of perfluorotributylamine to obtain a 10% solution by mass. The solution was applied to a quartz plate by spin coating, and the transmittance at 193nm was measured by an ultraviolet vacuum spectrometer to determine the light transmittance at 200nm as a converted coating film thickness of 95%. The refractive index of the coating film was measured to be 1.35 with an Abbe refractometer.
Obtained by F19 nuclear magnetic spectrum, based on CF 2 =CF（CF 2 ） 2 OCF=CF 2 Has a structural unit content of 19mol%, a structural unit content based on perfluoro (2, 2-dimethyl-1, 3-dioxole) of 53mol%, and a structural unit content based on C7PEVE of 28 mol%.
Example 3
An amorphous fluorine-containing polymer and a preparation method thereof, taking a 1000ml polymerization kettle as an example, 400g of deionized water and 10ml of 5wt% ammonium perfluorooctanoate water are added into a clean polymerization kettleSolution, 1g disodium hydrogen phosphate; and repeatedly performing nitrogen pressurization, evacuation and deoxygenation until the oxygen content is less than 30 ppm. Then the composition was 30mol% CF 2 =CF（CF 2 ） 2 OCF=CF 2 100g of a mixed monomer comprising 60mol% of perfluoro (2, 2-dimethyl-1, 3-dioxole) and 10mol% of EEEAVE was charged into a polymerization vessel. The polymerization kettle was heated to 90 ℃ and 8g of a 10% aqueous ammonium persulfate solution was pumped in to initiate the reaction while 1.3g of the chain transfer agent methanol was added. Emulsion polymerization is carried out for 15h at 90 ℃, the emulsion obtained by the reaction is coagulated by magnesium chloride aqueous solution, washed by deionized water and continuously dried for 20h in a vacuum oven at 90 ℃ and-0.09 MPa. Then, the terminal stabilization was carried out under a 20% fluorine gas atmosphere diluted with nitrogen at a pressure of 1.0MPa and a temperature of 150 ℃ for 7 hours. 94g of a fluoropolymer was finally obtained.
The polymer was dissolved in perfluoro (2-butyltetrahydrofuran) to give a 10% solution, and the intrinsic viscosity of the fluoropolymer was 0.055dL/g as measured at 30 ℃.
Measurement of fluoropolymer in fluorinated solvent HCF225cb (formula CClF) at 20 deg.C 2 CF 2 CHClF, boiling point 56 ℃), CH 3 CCl 2 F (boiling point 32 ℃ C.), CF 3 CH 2 OCF 2 CF 2 The solubilities of H (boiling point: 56 ℃) were 45g,25g and 35g, respectively.
10g of the above fluoropolymer was dissolved in 90g of perfluorotributylamine to obtain a 10% by mass solution. The solution was applied to a quartz plate by spin coating, and the transmittance at 193nm was measured by an ultraviolet vacuum spectrometer, and the transmittance was measured to be 96% in terms of the coating film thickness of 200 nm. The refractive index of the coating film was measured to be 1.32 with an Abbe refractometer.
Obtained by F19 nuclear magnetic spectrum, based on CF 2 =CF（CF 2 ） 2 OCF=CF 2 Has a structural unit content of 32mol%, a structural unit content of 57mol% based on perfluoro (2, 2-dimethyl-1, 3-dioxole), and a structural unit content of 1mol% based on EEEAVE.
Example 4
An amorphous fluorine-containing polymer and a preparation method thereof,taking a 1000ml polymerization kettle as an example, 400g of deionized water, 15ml of 5wt% ammonium perfluorooctanoate aqueous solution and 1g of disodium hydrogen phosphate are added into a clean polymerization kettle; the nitrogen pressurization and the evacuation and the oxygen removal are repeatedly carried out until the oxygen content is less than 30ppm, and the product is qualified. Then the composition was 40mol% CF 2 =CF（CF 2 ）OCF=CF 2 40mol% of perfluoro (4-methyl-1, 3-dioxol), 20mol% of CF 2 ＝CF-OCF 2- OCF 3 100g of the mixed monomer (2) was charged into a polymerization vessel. The polymerization kettle was heated to 80 ℃ and 5g of a 10% aqueous ammonium persulfate solution was pumped in to initiate the reaction while 1g of the chain transfer agent isopropanol was added. Emulsion polymerization is carried out for 20h at the temperature of 80 ℃, emulsion obtained by the reaction is coagulated by magnesium chloride aqueous solution, washed by deionized water and continuously dried for 20h in a vacuum oven at the temperature of 90 ℃ and the pressure of-0.09 MPa. Then, under a 20% fluorine gas atmosphere diluted with nitrogen gas, under the conditions of a pressure of 1.0MPa and a temperature of 150 ℃, the terminal stabilization process was completed for 3 hours. Finally, 95g of a fluoropolymer was obtained.
The polymer was dissolved in perfluoro (2-butyltetrahydrofuran) to give a 10% solution, and the intrinsic viscosity of the fluoropolymer was found to be 0.063 dL/g under 30 ℃ measurement conditions.
Measurement of fluoropolymer in fluorinated solvent HCF225cb (formula CClF) at 20 deg.C 2 CF 2 CHClF, boiling point 56 ℃), CH 3 CCl 2 F (boiling point 32 ℃ C.), CF 3 CH 2 OCF 2 CF 2 The solubilities of H (boiling point: 56 ℃ C.) were 40g,28g and 34g, respectively.
10g of the fluoropolymer was dissolved in 90g of perfluorotributylamine to obtain a 10% solution by mass. The solution was applied to a quartz plate by spin coating, and the transmittance at 193nm was measured by an ultraviolet vacuum spectrometer, and the transmittance was measured to be 95% when the coating film thickness was 200 nm. The refractive index of the coating film was measured to be 1.33 using an Abbe refractometer.
Obtained by F19 nuclear magnetic spectrum, based on CF 2 =CF（CF 2 ）OCF=CF 2 Has a structural unit content of 39mol% based on the structural unit content of perfluoroperfluoro (4-methyl-1, 3-dioxole) of 40mol% based on CF 2 ＝CF-OCF 2 -OCF 3 The content of the structural unit (b) is 21mol%.
Example 5
An amorphous fluorine-containing polymer and a preparation method thereof, taking a 1000ml polymerization kettle as an example, 400g of deionized water, 15ml of 5wt% ammonium perfluorooctanoate aqueous solution and 1g of disodium hydrogen phosphate are added into a clean polymerization kettle; the nitrogen pressurization and the evacuation and the oxygen removal are repeatedly carried out until the oxygen content is less than 30ppm, and the product is qualified. Then the composition was 40mol% CF 2 =CF（CF 2 ）OCF=CF 2 40mol% of perfluoro (4, 5-dimethyl-2, 2-dioxole), 20mol% 2 ＝CF-(OCF 2 CF(CF 3 )) 2 -OCF 2 CF 2 CF 3 100g of the mixed monomer (2) was charged into a polymerization vessel. The polymerization kettle was heated to 80 ℃ and 5g of a 10% aqueous ammonium persulfate solution was pumped in to initiate the reaction while 1g of the chain transfer agent isopropanol was added. Emulsion polymerization is carried out for 35h at 80 ℃, emulsion obtained by reaction is coagulated by magnesium chloride aqueous solution, washed by deionized water and continuously dried for 20h in a vacuum oven at 90 ℃ and-0.09 MPa. Then, under a 20% fluorine gas atmosphere diluted with nitrogen gas, the terminal stabilization was completed under a pressure of 1.0MPa and a temperature of 150 ℃ for 4 hours. 89g of a fluoropolymer was finally obtained.
The polymer was dissolved in perfluoro (2-butyltetrahydrofuran) to give a 10% solution, and the intrinsic viscosity of the fluoropolymer was 0.062dL/g as measured at 30 ℃.
Measurement of fluoropolymer in fluorinated solvent HCF225cb (formula CClF) at 20 deg.C 2 CF 2 CHClF, boiling point 56 ℃), CH 3 CCl 2 F (boiling point 32 ℃), CF 3 CH 2 OCF 2 CF 2 The solubilities of H (boiling point: 56 ℃ C.) were 40g,26g and 31g, respectively.
10g of the fluoropolymer was dissolved in 90g of perfluorotributylamine to obtain a 10% solution by mass. The solution was applied to a quartz plate by spin coating, and the transmittance at 193nm was measured by an ultraviolet vacuum spectrometer to determine the light transmittance at 200nm as a converted coating film thickness of 95%. The refractive index of the coating film was measured by Abbe refractometer to be 1.34.
Obtained by F19 NMR spectroscopy, based on CF 2 =CF（CF 2 ）OCF=CF 2 Has a structural unit content of 37 mol% based on perfluoro (4, 5-dimethyl-2, 2-dioxole) and a structural unit content of 39mol% based on CF 2 ＝CF-(OCF 2 CF(CF 3 )) 2 -OCF 2 CF 2 CF 3 The content of the structural unit (b) is 24 mol%.
Comparative example 1
An amorphous fluorine-containing polymer and a preparation method thereof, taking a 1000ml polymerization kettle as an example, 400g of deionized water, 15ml of 5wt% ammonium perfluorooctanoate aqueous solution and 1g of disodium hydrogen phosphate are added into a clean polymerization kettle; the nitrogen pressurization and the evacuation and the oxygen removal are repeatedly carried out until the oxygen content is less than 30ppm, and the product is qualified. Then the composition was 50mol% CF 2 =CF（CF 2 ） 2 OCF=CF 2 And 50mol% perfluoro (2, 2-dimethyl-1, 3-dioxole) to prepare 100g of mixed monomer, and adding the mixed monomer into a polymerization kettle. The polymerization kettle was heated to 80 ℃ and 5g of a 10% aqueous ammonium persulfate solution was pumped in to initiate the reaction while 1g of the chain transfer agent isopropanol was added. Emulsion polymerization is carried out for 20h at the temperature of 80 ℃, emulsion obtained by the reaction is coagulated by magnesium chloride aqueous solution, washed by deionized water and continuously dried for 20h in a vacuum oven at the temperature of 90 ℃ and the pressure of-0.09 MPa. Then, the terminal stabilization process was completed for 6 hours under an atmosphere of 20% fluorine gas diluted with nitrogen gas under a pressure of 1.0MPa and a temperature of 150 ℃. 94g of a fluoropolymer was finally obtained.
This polymer was dissolved in perfluoro (2-butyltetrahydrofuran) to give a 10% solution, and the intrinsic viscosity of the fluoropolymer was 0.049dL/g as measured at 30 ℃.
Measurement of fluoropolymer in fluorinated solvent HCF225cb (formula CClF) at 20 deg.C 2 CF 2 CHClF, boiling point 56 ℃), CH 3 CCl 2 F (boiling point 32 ℃ C.), CF 3 CH 2 OCF 2 CF 2 The solubilities of H (boiling point: 56 ℃ C.) were 18g,13g and 16g, respectively.
10g of the above fluoropolymer was dissolved in 90g of perfluorotributylamine to obtain a 10% by mass solution. The solution was applied to a quartz plate by spin coating, and the transmittance at 193nm was measured by an ultraviolet vacuum spectrometer, and the transmittance was measured to be 95% when the coating film thickness was 200 nm. The refractive index of the coating film was measured to be 1.33 using an Abbe refractometer.
Obtained by F19 nuclear magnetic spectrum, based on CF 2 =CF（CF 2 ） 2 OCF=CF 2 Has a structural unit content of 52mol% based on the structural unit content of perfluoro (2, 2-dimethyl-1, 3-dioxole) of 48mol%.
Comparative example 2
An amorphous fluorine-containing polymer and a preparation method thereof, taking a 1000ml polymerization kettle as an example, 400g of deionized water, 15ml of 5wt% ammonium perfluorooctanoate aqueous solution and 1g of disodium hydrogen phosphate are added into a clean polymerization kettle; the nitrogen pressurization and the evacuation and the oxygen removal are repeatedly carried out until the oxygen content is less than 30ppm, and the product is qualified. Then adding CF 2 =CF（CF 2 ） 2 OCF=CF 2 100g of monomers are added into a polymerization kettle. The polymerization kettle was heated to 80 ℃ and 5g of a 10% aqueous ammonium persulfate solution was pumped in to initiate the reaction while 1g of the chain transfer agent isopropanol was added. Emulsion polymerization is carried out for 20h at 80 ℃, the emulsion obtained by the reaction is coagulated by magnesium chloride aqueous solution, washed by deionized water and continuously dried for 20h in a vacuum oven at 90 ℃ and-0.09 MPa. Then, the terminal stabilization process was completed for 5 hours under an atmosphere of 20% fluorine gas diluted with nitrogen gas under a pressure of 1.0MPa and a temperature of 150 ℃. Finally, 92g of a fluoropolymer was obtained.
The polymer was dissolved in perfluoro (2-butyltetrahydrofuran) to give a 10% solution, and the intrinsic viscosity of the fluoropolymer was 0.051dL/g as measured at 30 ℃.
10g of the above-mentioned fluoropolymer was dissolved in 90g of perfluorotributyl amine to obtain a 10% by mass solution. The solution was applied to a quartz plate by spin coating, and the transmittance at 193nm was measured by an ultraviolet vacuum spectrometer to obtain a light transmittance of 91% in terms of the coating film thickness of 200 nm. The refractive index of the coating film was measured to be 1.36 using an Abbe refractometer.
Measurement of fluoropolymer in fluorinated solvent HCF225cb (formula CClF) at 20 deg.C 2 CF 2 CHClF, boiling point 56 ℃), CH 3 CCl 2 F (boiling point 32 ℃ C.), CF 3 CH 2 OCF 2 CF 2 The solubilities of H (boiling point: 56 ℃) were 19g,14g and 17g, respectively.
Comparative example 3
An amorphous fluorine-containing polymer and a preparation method thereof, taking a 1000ml polymerization kettle as an example, 400g of deionized water, 15ml of 5wt% ammonium perfluorooctanoate aqueous solution and 1g of disodium hydrogen phosphate are added into a clean polymerization kettle; the nitrogen pressurization and the evacuation and the oxygen removal are repeatedly carried out until the oxygen content is less than 30ppm, and the product is qualified. Then the addition composition was 25mol% CF 2 =CF（CF 2 ） 2 OCF=CF 2 100g of a mixed monomer containing 25mol% of perfluoro (2, 2-dimethyl-1, 3-dioxole) and 50mol% of C9PEVE was charged into a polymerization vessel. The polymerization kettle was heated to 80 ℃ and 5g of a 10% aqueous ammonium persulfate solution was pumped in to initiate the reaction while 1g of the chain transfer agent isopropanol was added. Emulsion polymerization is carried out for 23h at 80 ℃, the emulsion obtained by the reaction is coagulated by magnesium chloride aqueous solution, washed by deionized water and continuously dried for 20h in a vacuum oven at 90 ℃ and-0.09 MPa. Then, the terminal stabilization was carried out under a 20% fluorine gas atmosphere diluted with nitrogen at a pressure of 1.0MPa and a temperature of 150 ℃ for 4 hours. Finally, 92g of a fluoropolymer was obtained.
The polymer was dissolved in perfluoro (2-butyltetrahydrofuran) to give a 10% solution, and the intrinsic viscosity of the fluoropolymer was 0.058dL/g as measured at 30 ℃.
Measurement of fluoropolymer in fluorinated solvent HCF225cb (formula CClF) at 20 deg.C 2 CF 2 CHClF, boiling point 56 ℃), CH 3 CCl 2 F (boiling point 32 ℃ C.), CF 3 CH 2 OCF 2 CF 2 The solubilities of H (boiling point: 56 ℃ C.) were 32g,21g and 26g, respectively.
10g of the fluoropolymer was dissolved in 90g of perfluorotributylamine to obtain a 10% solution by mass. The solution was applied to a quartz plate by spin coating, and the transmittance at 193nm was measured by an ultraviolet vacuum spectrometer, and the transmittance was 87% in terms of the coating film thickness of 200 nm. The refractive index of the coating film was measured to be 1.39 using an Abbe refractometer.
Obtained by F19 nuclear magnetic spectrum, based on CF 2 =CF（CF 2 ） 2 OCF=CF 2 Has a structural unit content of 26 mol% based on the structural unit content of perfluoro (2, 2-dimethyl-1, 3-dioxole) of 25mol%; the content of structural units based on C9PEVE was 49mol%.
Comparative example 4
Taking a 1000ml polymerization kettle as an example, 400g of deionized water, 15ml of 5wt% ammonium perfluorooctanoate aqueous solution and 1g of disodium hydrogen phosphate are added into a clean polymerization kettle; the nitrogen pressurization and the evacuation and the oxygen removal are repeatedly carried out until the oxygen content is less than 30ppm, and the product is qualified. Then adding the composition 40mol% CF 2 =CF（CF 2 ） 2 OCF=CF 2 100g of a mixed monomer was prepared by mixing 40mol% of perfluoro (2, 2-dimethyl-1, 3-dioxole) and 20mol% of C9PEVE, and the mixture was charged into a polymerization vessel. The polymerization kettle was heated to 80 ℃ and 2g of a 10% aqueous ammonium persulfate solution was pumped in to initiate the reaction. Emulsion polymerization is carried out for 30h at the temperature of 80 ℃, emulsion obtained by the reaction is coagulated by magnesium chloride aqueous solution, washed by deionized water and continuously dried for 20h in a vacuum oven at the temperature of 90 ℃ and the pressure of-0.09 MPa, and finally 86g of fluorine-containing polymer is obtained.
This polymer was dissolved in perfluoro (2-butyltetrahydrofuran) to give a 10% solution, and the intrinsic viscosity of the fluoropolymer was 0.13dL/g as measured at 30 ℃.
The fluoropolymer was measured in a fluorine-containing solvent HCF225cb (formula CClF) at 20 deg.C 2 CF 2 CHClF, boiling point 56 ℃), CH 3 CCl 2 F (boiling point 32 ℃ C.), CF 3 CH 2 OCF 2 CF 2 The solubilities of H (boiling point: 56 ℃) were 12g,8g and 11g, respectively.
10g of the above-mentioned fluoropolymer was dissolved in 90g of perfluorotributyl amine to obtain a 10% by mass solution. The solution was applied to a quartz plate by spin coating, and the transmittance at 193nm was measured by an ultraviolet vacuum spectrometer, and the transmittance was 69% in terms of the coating film thickness of 200 nm. The refractive index of the coating film was measured to be 1.42 using an Abbe refractometer.
By F19 nuclear magnetic spectrumGraph obtained based on CF 2 =CF（CF 2 ） 2 OCF=CF 2 Has a structural unit content of 38mol%, a structural unit content of 39mol% based on perfluoro (2, 2-dimethyl-1, 3-dioxole), and a structural unit content of 23mol% based on C9 PEVE.
Comparative example 5
Taking a 1000ml polymerization kettle as an example, 400g of deionized water, 15ml of 5wt% ammonium perfluorooctanoate aqueous solution and 1g of disodium hydrogen phosphate are added into a clean polymerization kettle; the nitrogen pressurization and the evacuation and the oxygen removal are repeatedly carried out until the oxygen content is less than 30ppm, and the product is qualified. Then the composition is 80mol% CF 2 =CF（CF 2 ） 2 OCF=CF 2 100g of mixed monomers of 20mol% C9PEVE was charged into a polymerization vessel. The polymerization kettle was heated to 70 ℃ and 5g of a 10% aqueous ammonium persulfate solution was pumped in to initiate the reaction while 1g of the chain transfer agent isopropanol was added. Emulsion polymerization is carried out for 25h at 70 ℃, emulsion obtained by reaction is coagulated by magnesium chloride aqueous solution, washed by deionized water and continuously dried for 20h in a vacuum oven at 90 ℃ and-0.09 MPa. Then, the terminal stabilization process was completed under an atmosphere of 20% fluorine gas diluted with nitrogen gas at a pressure of 1.0MPa and a temperature of 150 ℃ for 15 hours. 94g of a fluoropolymer was finally obtained.
This polymer was dissolved in perfluoro (2-butyltetrahydrofuran) to give a 10% solution, and the intrinsic viscosity of the fluoropolymer was 0.066dL/g as measured at 30 ℃.
Measurement of fluoropolymer in fluorinated solvent HCF225cb (formula CClF) at 20 deg.C 2 CF 2 CHClF, boiling point 56 ℃), CH 3 CCl 2 F (boiling point 32 ℃), CF 3 CH 2 OCF 2 CF 2 The solubilities of H (boiling point: 56 ℃) were 23g,18g and 21g, respectively.
10g of the above fluoropolymer was dissolved in 90g of perfluorotributylamine to obtain a 10% by mass solution. The solution was applied to a quartz plate by spin coating, and the transmittance at 193nm was measured by an ultraviolet vacuum spectrometer, and the transmittance was measured to be 73% in terms of the coating film thickness of 200 nm. The refractive index of the coating film was measured by Abbe refractometer to be 1.36.
Obtained by F19 nuclear magnetic spectrum, based on CF 2 =CF（CF 2 ） 2 OCF=CF 2 The content of structural units of (2) is 77mol%, and the content of structural units based on C9PEVE is 23mol%.
TABLE 1 results of Performance test of amorphous fluoropolymers obtained in examples 1-5
TABLE 2 results of performance testing of amorphous fluoropolymers obtained in comparative examples 1-5
The above-mentioned embodiments are intended to illustrate the technical solutions and advantages of the present invention, and it should be understood that the above-mentioned embodiments are only specific embodiments of the present invention, and are not intended to limit the present invention, and any modifications, additions, equivalents, etc. made within the scope of the principles of the present invention should be included in the scope of the present invention.
Claims (14)
1. An amorphous polymer having structural units A based on a perfluorodiene of formula I, structural units B based on a perfluoroheterocycloalkylene monomer and structural units C based on formula II; content of structural units a, B, C: 18-40 mol% of A structural unit, 38-60mol% of B structural unit and 10-30mol% of C structural unit;
wherein, formula I: CF (compact flash) 2 =CF（CF 2 ） n OCF=CF 2 N is 1 or 2, and n is,
formula II: CF (compact flash) 2 ＝CF(OR f2 ) q -(OCF 2 ) m -OR f5 Wherein R is f2 Is C2-C4 perfluoroalkyl, R f5 Is perfluoroalkyl group having 1 to 4 carbon atoms, q is an integer of 0 to 3, m is an integer of 0 to 4, and q + m is an integer of 1 to 7.
2. The amorphous polymer of claim 1, wherein the perfluoroheterocycloalkene monomer comprises at least one of perfluoro (2, 2-dimethyl-1, 3-dioxole), perfluoro (4-methyl-1, 3-dioxole), perfluoro (2, 3-dimethyl-1, 3-dioxole), perfluoro (4, 5-dimethyl-2, 2-dioxole), perfluoro (2, 3-dimethyl-1, 4-dioxine).
3. An amorphous polymer according to claim 1 wherein the monomer of formula ii is selected from one of the following:
CF 2 =CF-OCF 2 CF 2 -(OCF 2 ) 4 -OCF 3 、CF 2 ＝CF-OCF 2 CF 2 -(OCF 2 ) 2 -OCF 3 、CF 2 =CF-(OCF 2 CF 2 ) 2 -OCF 2 CF 3 、CF 2 =CF-(OCF 2 CF 2 ) 3 -OCF 2 CF 3 、CF 2 =CF-OCF 2 -OCF 3 、CF 2 ＝CF-OCF 2 -OCF 2 CF 3 、
CF 2 ＝CF-(OCF 2 CF(CF 3 ) 2 ) 2 -OCF 2 CF 2 CF 3 、CF 2 ＝CF-(OCF 2 ) 2 -OCF 3 。
4. the amorphous polymer of claim 3 wherein the monomer of formula II is selected from CF 2 =CF-OCF 2 CF 2 -(OCF 2 ) 4 -OCF 3 、CF 2 ＝CF-OCF 2 CF 2 -(OCF 2 ) 2 -OCF 3 、CF 2 =CF-(OCF 2 CF 2 ) 2 - OCF 2 CF 3 、CF 2 =CF-(OCF 2 CF 2 ) 3 -OCF 2 CF 3 One kind of (1).
5. The amorphous polymer of claim 1, wherein the amorphous polymer has an intrinsic viscosity in the range of 0.04 to 0.12dL/g per fluoro (2-butyltetrahydrofuran) at 30 ℃.
6. The amorphous polymer of claim 5, wherein the amorphous polymer has an intrinsic viscosity in perfluoro (2-butyltetrahydrofuran) in the range of 0.05 to 0.10dL/g at 30 ℃.
7. The amorphous polymer of claim 1, wherein the amorphous fluoropolymer has a light transmittance of 95 to 97% and a refractive index of 1.3 to 1.35.
8. A method for preparing an amorphous fluoropolymer, comprising the steps of:
mixing water, an emulsifier and a pH regulator, deoxidizing, and adding a mixed monomer; then adding an initiator and a chain transfer agent, carrying out polymerization reaction at 50-120 ℃, and carrying out coagulation or precipitation, drying and end group stabilization treatment on the emulsion after the polymerization reaction to obtain the amorphous fluorine-containing polymer.
9. The method for preparing an amorphous polymer according to claim 8, wherein at least one of the following conditions is satisfied:
(1) The reaction temperature is 60-100 ℃, and the reaction time is 15-35 hours;
(2) The emulsifier is at least one of ammonium perfluorooctanoate and sodium perfluorooctanoate, and the addition amount of the emulsifier is 0.1-2% of the mass of water;
(3) The pH regulator is at least one of disodium hydrogen phosphate and dipotassium hydrogen phosphate, and the addition amount of the pH regulator is 0.01-0.5% of the mass of water;
(4) The chain transfer agent is one or more of dodecyl mercaptan, isopropanol, methanol, ethanol, isopentane or acetone; the adding amount of the chain transfer agent is 0.5-1.5 percent of the mass of the mixed monomer,
(5) The addition amount of the initiator is 0.2-1% of the mass of the mixed monomer;
(6) The mixed monomer comprises the following raw materials in percentage by weight: 20-40 mol% of monomer I, 40-60mol% of perfluoroheterocyclic alkene monomer and 10-35mol% of monomer II;
(7) The method for stabilizing the end group comprises the following steps: the dried product was treated under a 20% fluorine gas atmosphere diluted with nitrogen at a pressure of 1.0MPa and a temperature of 150 ℃ for 2 to 8 hours.
10. The method for preparing an amorphous polymer according to claim 9, wherein at least one of the following conditions is satisfied:
the reaction temperature is 70-90 ℃;
(ii) the addition amount of the pH regulator is 0.2-0.3% of the mass of water;
(iii) the amount of chain transfer agent added is 0.7-1.3% of the mass of the mixed monomers;
(iv) the amount of the initiator added is 0.4 to 0.8% by mass of the mixed monomers.
11. A composition comprising the amorphous polymer according to any one of claims 1 to 7 or the amorphous polymer produced by the production method according to any one of claims 8 to 10, wherein the composition is composed of the amorphous polymer and a fluorine-containing solvent, the amorphous polymer is present in the composition in an amount of 0.1 to 40% by mass, and the fluorine-containing solvent has 2 or more carbon atoms, 1 to 20 fluorine atoms, and a boiling point of 30 to 160 ℃.
12. The composition as claimed in claim 11, wherein the fluorine-containing solvent is a solvent containing 2 to 6 carbon atoms and 1 to 10 fluorine atoms.
13. The composition of claim 11, wherein the fluorine-containing solvent is selected from the group consisting of CH 3 CCl 2 F、CF 3 (CF 2 ) 3 CH 2 CH 3 、CF 3 (CF 2 ) 3 OCH 3 、CF 3 (CHF) 2 CF 2 CF 3 、CF 3 CH 2 OCF 2 CHF 2 、CClF 2 CF 2 CHFCl、(CF 3 ) 2 CHOH、CF 3 CF 2 CHCl 2 、CF 3 CF 2 CF 2 CHCl 2 、CClF 2 CF 2 CHClF、CF 3 CF 2 CHFCHFCF 3 、CF 3 CF 2 CF 2 CF 2 CH 2 CH 3 、CF 3 CF 2 CF 2 OCH 3 、CF 3 CF 2 CF 2 OC 2 H 5 Or CF 3 CH 2 OCF 2 CF 2 H, one or more of H.
14. Use of an amorphous polymer according to any one of claims 1 to 7 or prepared by a process according to any one of claims 8 to 10 in an optical material.
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| US5111526A (en) * | 1990-01-19 | 1992-05-05 | Mitsubishi Rayon Co., Ltd. | Plastic optical fibers and process for the production thereof |
| CN103864979A (en) * | 2014-03-06 | 2014-06-18 | 山东华夏神舟新材料有限公司 | Fluorine-containing polymer and preparation method thereof |
| CN108517025A (en) * | 2018-03-23 | 2018-09-11 | 博容新材料（深圳）有限公司 | A kind of amorphous fluoropolymer and preparation method thereof |
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| US5111526A (en) * | 1990-01-19 | 1992-05-05 | Mitsubishi Rayon Co., Ltd. | Plastic optical fibers and process for the production thereof |
| CN103864979A (en) * | 2014-03-06 | 2014-06-18 | 山东华夏神舟新材料有限公司 | Fluorine-containing polymer and preparation method thereof |
| CN108517025A (en) * | 2018-03-23 | 2018-09-11 | 博容新材料（深圳）有限公司 | A kind of amorphous fluoropolymer and preparation method thereof |
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