Amorphous fluorine-containing copolymer and application thereof in preparation of perfluororesin film

Abstract

The invention discloses an amorphous fluorine-containing copolymer and application thereof in preparation of a perfluororesin film, and belongs to the technical field of polymer materials. The invention provides the amorphous fluorine-containing copolymer, and the perfluororesin film prepared from the amorphous fluorine-containing copolymer has waterproof and breathable effects in high performance liquid chromatography detection, can obviously improve the detection precision and the detection efficiency, and is long in service life and convenient to use. The perfluororesin film is prepared by an injection molding process. The perfluororesin film has the characteristics of high air permeability, high light transmittance, low refractive index, low release force, high temperature resistance, high chemical stability, good biocompatibility, high hydrophobicity and excellent physical properties.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials, and in particular relates to an amorphous fluorine-containing copolymer and application thereof in preparing a perfluorinated resin film. Background Art

[0002] Amorphous fluorinated polymers have the characteristics of high transparency, low refractive index, low surface tension, etc. They are soluble in specific solvents and can be coated, impregnated, etc. to produce low refractive index coatings for optical devices.

[0003] However, traditional films or tubes have leakage during use, and their overall service life is not long. The ventilation effect is not ideal, resulting in large errors in detection accuracy, small gas flux of the tube, and inefficient detection. Summary of the invention

[0004] The first purpose of the present invention is to provide an amorphous fluorinated copolymer, and the perfluororesin film prepared from the amorphous fluorinated copolymer plays a role of water-proof and breathable in high performance liquid chromatography detection, which can significantly improve the detection accuracy and detection efficiency, and at the same time has a long service life and is easy to use.

[0005] The second object of the present invention is to provide a perfluororesin film, which is prepared by injection molding and has the characteristics of high air permeability, high chemical stability, good biocompatibility, high hydrophobicity and excellent physical properties.

[0006] The present invention is achieved through the following technical solutions:

[0007] An amorphous fluorinated copolymer, the chemical structural formula of the fluorinated copolymer is as follows:

[0008]

[0009] Among them, x, y, and z are all natural numbers not less than 0.

[0010] Preferably, the structural formula of A in the structural formula is:

[0011]

[0012] Here, G1, G2, G3, and G4 are each a fluorine atom or a C1-C6 fluorine-containing alkyl group.

[0013] Preferably, the structural formula of B in the structural formula is:

[0014]

[0015] Wherein, R1, R2, R3, R4, R5 and R6 are fluorine atoms or C1-C6 fluorine-containing alkyl groups;

[0016] m is 0, 1 or 2.

[0017] Preferably, the structural formula of C in the structural formula is any one of the following five fluorine-containing or perfluorinated structures;

[0018]

[0019] Preferably, the molecular weight of the amorphous fluorine-containing copolymer is in the range of 200,000-2,000,000.

[0020] A method for preparing an amorphous fluorine-containing copolymer. The amorphous fluorine-containing copolymer is prepared by any one of bulk polymerization, solution polymerization and emulsion polymerization.

[0021] The invention discloses an application of an amorphous fluorine-containing copolymer in preparing a perfluorinated resin film.

[0022] A perfluororesin film comprises the amorphous fluorine-containing copolymer.

[0023] A method for preparing a perfluororesin film comprises the following steps:

[0024] S1. Ingredients:

[0025] The amorphous fluorinated copolymer as claimed in claim 1 is placed in a vacuum oven at 100-120° C. and dried for 7-8 hours, then mixed with a perfluorinated solvent at a weight ratio of 1-20%:1, heated to 75-80° C., and stirred until completely dissolved to obtain an amorphous fluorinated copolymer solution;

[0026] The amorphous fluorinated copolymer solution is finely filtered through a 10-15 μm filter into a liquid feed device of an injection device, and vacuum degassed at a constant temperature of 75° C. for standby use;

[0027] S2. Mould surface treatment:

[0028] Clean the silicon substrate mold in an ultrasonic cleaning machine to ensure that the substrate surface is free of dirt, then perform plasma treatment on the surface, spray a low-release fluorine coating, and bake in an oven at 120-150°C for 25-30 minutes;

[0029] S3, Workstation preparation:

[0030] Put the silicon-based substrate mold treated with S2 into the mold and place them together in a clean baking device to adjust the substrate level and clean the surface of the silicon-based substrate mold; after cleaning, start constant temperature heating at 60°C;

[0031] S4, injection:

[0032] Slowly open the baking equipment door, slowly extend the injection device to the top of the mold in the baking equipment and inject the material;

[0033] After the injection is completed, the injection device is retracted and the ultrasonic device under the mold is turned on to assist leveling;

[0034] S5. Baking:

[0035] Set the temperature of the baking equipment to 120-150°C, maintain the vacuum state for 8-10 minutes, then start the solvent recovery device, stop the recovery after 2-3 minutes of air intake recovery, and maintain the vacuum state for 10-15 minutes again, and repeat this cycle until the solution is completely dry;

[0036] S6, peeling:

[0037] The glass substrate with the dry film on the surface after S5 treatment is cooled to room temperature, and trimmed. The film on the four sides of the substrate is slowly peeled off by a trimming device until the film is completely peeled off;

[0038] S7, Lamination:

[0039] After the film is dusted, it is placed horizontally on the conveyor belt of the laminating device, and the laminating device is turned on to perform double-sided lamination protection on the film.

[0040] Preferably, in S1, the perfluorinated solvent is 3M-FC40 fluorinated liquid;

[0041] In S2, the thickness of the low-release fluorine coating is 5 to 100 nm;

[0042] In S4, the injection time is 3 to 15 seconds.

[0043] The above-mentioned low-release fluorine coating is a release coating, which acts like a release agent and facilitates the intact peeling of the formed film from the mold.

[0044] In the above injection steps, the injection time is generally between 3 and 15 seconds, which needs to be adjusted according to the solid content and viscosity of the solution and the mold temperature to achieve the best injection effect. The thickness is determined according to the thickness of the required film. The flow rate is generally considered to be optimal when no splashing or impact bubbles are generated.

[0045] In the above baking step, a solvent recovery device is provided. As the film is baking and the solvent evaporates, the solvent concentration in the enclosed space of the oven will continue to increase with the baking time and the increase in baking temperature. At this time, equipment is needed to recover the solvent in the oven space so that the solvent concentration in the oven is always in an optimal range. This range is between 10% and 45%.

[0046] Compared with the prior art, the present invention has at least the following technical effects:

[0047] The present invention provides an amorphous fluorine-containing copolymer, and the perfluororesin film prepared from the amorphous fluorine-containing copolymer plays a role of water-proofing and air-permeability in high performance liquid chromatography detection, can significantly improve detection accuracy and detection efficiency, and has a long service life and is easy to use.

[0048] The perfluororesin film is prepared by injection molding and has the characteristics of high air permeability, high light transmittance, low refractive index, low release force, high temperature resistance, high chemical stability, good biocompatibility, high hydrophobicity and excellent physical properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0049] Figure 1 This is a DSC test curve diagram for the material prepared in Example 2. DETAILED DESCRIPTION

[0050] The embodiments of the present invention will be described in detail below in conjunction with examples. However, those skilled in the art will understand that the following examples are only used to illustrate the present invention and should not be construed as limiting the scope of the present invention. The specific conditions not specified in the examples are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used without indicating the manufacturer are all conventional products that can be purchased commercially.

[0051] A technical solution of a specific implementation of the present invention is:

[0052] An amorphous fluorinated copolymer, the chemical structural formula of the fluorinated copolymer is as follows:

[0053]

[0054] Among them, x, y, and z are all natural numbers not less than 0.

[0055] Preferably, the structural formula of A in the structural formula is:

[0056]

[0057] Here, G1, G2, G3, and G4 are each a fluorine atom or a C1-C6 fluorine-containing alkyl group.

[0058] Preferably, the structural formula of B in the structural formula is:

[0059]

[0060] Wherein, R1, R2, R3, R4, R5 and R6 are fluorine atoms or C1-C6 fluorine-containing alkyl groups;

[0061] m is 0, 1 or 2.

[0062] Preferably, the structural formula of C in the structural formula is any one of the following five fluorine-containing or perfluorinated structures;

[0063]

[0064] Preferably, the molecular weight of the amorphous fluorine-containing copolymer is in the range of 200,000-2,000,000.

[0065] A method for preparing an amorphous fluorine-containing copolymer. The amorphous fluorine-containing copolymer is prepared by any one of bulk polymerization, solution polymerization and emulsion polymerization.

[0066] The invention discloses an application of an amorphous fluorine-containing copolymer in preparing a perfluorinated resin film.

[0067] A perfluororesin film comprises the amorphous fluorine-containing copolymer.

[0068] A method for preparing a perfluororesin film comprises the following steps:

[0069] S1. Ingredients:

[0070] The amorphous fluorinated copolymer as claimed in claim 1 is placed in a vacuum oven at 100-120° C. and dried for 7-8 hours, then mixed with a perfluorinated solvent at a weight ratio of 1-20%:1, heated to 75-80° C., and stirred until completely dissolved to obtain an amorphous fluorinated copolymer solution;

[0071] The amorphous fluorinated copolymer solution is finely filtered through a 10-15 μm filter into a liquid feed device of an injection device, and vacuum degassed at a constant temperature of 75° C. for standby use;

[0072] S2. Mould surface treatment:

[0073] Clean the glass substrate in an ultrasonic cleaning machine, make sure the surface of the substrate is free of dirt, then perform plasma treatment on the surface, spray a low-release fluorine coating, and bake it in an oven at 120-150°C for 25-30 minutes;

[0074] S3, Workstation preparation:

[0075] Put the silicon-based substrate mold treated with S2 into the mold and place them together in a clean baking device to adjust the substrate level and clean the surface of the silicon-based substrate mold; after cleaning, start constant temperature heating at 60°C;

[0076] S4, injection:

[0077] Slowly open the baking equipment door, slowly extend the injection device to the top of the mold in the baking equipment and inject the material;

[0078] After the injection is completed, the injection device is retracted and the ultrasonic device under the mold is turned on to assist leveling;

[0079] S5. Baking:

[0080] Set the temperature of the baking equipment to 120-150°C, maintain the vacuum state for 8-10 minutes, then start the solvent recovery device, stop the recovery after 2-3 minutes of air intake recovery, and maintain the vacuum state for 10-15 minutes again, and repeat this cycle until the solution is completely dry;

[0081] S6, peeling:

[0082] The silicon-based substrate mold with the dry film on the surface after S5 treatment is cooled to room temperature, and trimmed. The films on the four sides of the substrate are slowly peeled off with a trimming device until the films are completely peeled off;

[0083] S7, Lamination:

[0084] After the film is dusted, it is placed horizontally on the conveyor belt of the laminating device, and the laminating device is turned on to perform double-sided lamination protection on the film.

[0085] Preferably, in S1, the perfluorinated solvent is 3M-FC40 fluorinated liquid;

[0086] In S2, the thickness of the low-release fluorine coating is 5 to 100 nm;

[0087] In S4, the injection time is 3 to 15 seconds.

[0088] Embodiment 1:

[0089] A method for preparing an amorphous fluorine-containing copolymer adopts a bulk polymerization method, comprising injecting 20g of perfluoro 5-methyl-2-methylene-1,3-dioxane and 30g of perfluoro 2,2-dimethyl-1,3-dioxole into a 200 ml stainless steel reactor (nickel-plated on the inner layer), cooling to minus 60 degrees Celsius for vacuum deoxygenation, injecting nitrogen, and then injecting 3.5 grams of tetrafluoroethylene. 0.15 grams of perfluoroperoxypropionyl is pre-dissolved in 5 grams of Sikang F-8328 solvent, and after complete dissolution, the solution is injected into the reactor, and the nitrogen is pressurized to 10 atmospheres, and then the reaction system is slowly heated from room temperature to 50 degrees Celsius for 6 hours. After the reactor is opened, a white sponge-like copolymer is obtained, and 41 grams of powdered product is obtained after vacuum drying, with a conversion rate of about 75%.

[0090] Example 2

[0091] A method for preparing an amorphous fluorine-containing copolymer adopts a solution polymerization method, comprising injecting 10g of perfluoro 4-methyl-2-methylene-1,3-dioxolane, 40g of perfluoro 2,2-dimethyl-1,3-dioxolane, 5g of trifluoromethyl trifluorovinyl ether and 200g of Scon F-8328 solvent into a 200ml stainless steel reactor (nickel-plated inner layer), cooling to minus 60 degrees Celsius for vacuum deoxygenation, and then injecting nitrogen, followed by injecting 3.5g of tetrafluoroethylene. 0.15g of perfluoro propionyl peroxide is pre-dissolved in 5g of Scon F-8328 solvent, and after complete dissolution, the solution is injected into the reactor, and the nitrogen is pressurized to 10 atmospheres, and then the reaction system is slowly heated from room temperature to 50 degrees Celsius for 6 hours. After the reactor is opened, a white filamentous copolymer is obtained, and 46.5g of powdered product is obtained after vacuum drying, with a conversion rate of about 84%.

[0092] The above-mentioned Sikang F-8328 solvent is used to dissolve, disperse and mix the materials to make their polymerization reaction more complete.

[0093] Example 3

[0094] A method for preparing an amorphous fluorine-containing copolymer adopts an emulsion polymerization method, comprising injecting 20g of perfluoro 5-methyl-2-methylene-1,3-dioxane, 30g of perfluoro 2,2-dimethyl-1,3-dioxole, 2g of GenX surfactant of DuPont, USA, and 200ml of deionized water into a 1-liter stainless steel reactor (nickel-plated inner layer), purging with nitrogen for 20 minutes at about 0 degrees Celsius to deoxidize, and then injecting 5g of CTFE. 20ml of 2% ammonium persulfate solution is injected into the reactor, and nitrogen is pressurized to 5 atmospheres, and then the reaction system is slowly heated from room temperature to 60 degrees Celsius and reacted for 8 hours. After the reactor is opened, a translucent hard copolymer is obtained, and 38.8g of powdered product is obtained after vacuum drying, and the conversion rate is about 70%.

[0095] Embodiment 4:

[0096] A method for preparing a perfluororesin film comprises the following steps:

[0097] S1: Ingredients: After the prepared amorphous fluorinated copolymer is placed in a vacuum oven and dried at 120°C for 8 hours, it is mixed with a perfluorinated solvent at a weight ratio of 1-20%:1, the temperature is raised to 75°C, and stirred until completely dissolved. The prepared amorphous fluorinated copolymer solution is finely filtered at 10μm into the feed liquid device of the injection equipment, and maintained at a constant temperature of 75°C for vacuum degassing before use.

[0098] S2: Mould surface treatment: Clean the glass substrate in an ultrasonic cleaning machine to ensure that the surface of the substrate is free of dirt, then perform plasma treatment on the surface, spray a low-release fluorine coating, and bake in an oven at 150°C for 30 minutes.

[0099] S3: Workstation preparation: Place the surface treated silicon substrate mold into the mold and place it together in a clean baking device to adjust the substrate level and clean the surface of the silicon substrate mold. After cleaning, start constant temperature heating at 60°C.

[0100] S4: Injection: Slowly open the baking equipment door, slowly extend the injection device to the top of the mold in the baking equipment and inject the material. After the injection is completed, retract the injection device and turn on the ultrasonic device under the mold to assist leveling.

[0101] S5: Baking: Set the temperature of the baking equipment to 150°C, maintain the vacuum state for 10 minutes, turn on the solvent recovery device, stop the recovery after 2 minutes of air intake recovery, and maintain the vacuum state for another 10 minutes, and repeat this cycle until the solution is completely dry.

[0102] S6: Peeling: The silicon-based substrate mold with the dry film on the surface is cooled to room temperature, and trimmed. The films on the four sides of the substrate are slowly peeled off with a trimming device until the film is completely peeled off.

[0103] S7: Laminating: After dust removal, the film is placed horizontally on the conveyor belt of the laminating device, and the laminating device is turned on to perform double-sided lamination protection on the film.

[0104] S8: Cutting: According to different customer needs, layout and cutting are carried out on the CNC cutting table.

[0105] Table 1 Perfluororesin film product standards

[0106]

[0107] like Figure 1 , which is a DSC test curve of the amorphous fluorinated copolymer prepared in Example 2.

[0108] The results show that the glass transition temperature of the amorphous fluorine-containing copolymer prepared in Example 2 is between 260 and 275° C., proving that the material has extremely high heat resistance.

[0109] The curve shows a process of first heating up, then cooling down, and then heating up again.

[0110] Finally, it should be noted that the above description is only a preferred embodiment of the present invention and is not intended to limit the protection scope of the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. An amorphous fluorinated copolymer, characterized in that: The chemical structural formula of the fluorinated copolymer is as follows: Among them, x, y, and z are all natural numbers not less than 0.

2. The amorphous fluorinated copolymer according to claim 1, characterized in that: The structural formula of A in the structural formula is: Here, G1, G2, G3, and G4 are each a fluorine atom or a C1-C6 fluorine-containing alkyl group.

3. The amorphous fluorinated copolymer according to claim 1, characterized in that: The structural formula of B in the structural formula is: Among them, R1, R2, R3, R4, R5 and R6 are fluorine atoms or C1-C6 fluorine-containing alkyl groups; m is 0, 1 or 2.

4. The amorphous fluorinated copolymer according to claim 1, characterized in that: The structural formula of C in the structural formula is any one of the following five fluorine-containing or perfluorinated structures; 5. The amorphous fluorinated copolymer according to any one of claims 1 to 4, characterized in that The molecular weight of the amorphous fluorine-containing copolymer is in the range of 200,000-2,000,000.

6. A method for preparing an amorphous fluorinated copolymer according to any one of claims 1 to 4, characterized in that: The amorphous fluorine-containing copolymer is prepared by any one of bulk polymerization, solution polymerization and emulsion polymerization.

7. Use of the amorphous fluorinated copolymer according to any one of claims 1 to 4 in the preparation of a perfluororesin film.

8. A perfluororesin film, characterized in that: The invention comprises the amorphous fluorinated copolymer according to any one of claims 1 to 4.

9. A method for preparing a perfluororesin film as claimed in claim 8, characterized in that: The steps include: S1. Ingredients: The amorphous fluorinated copolymer as claimed in claim 1 is placed in a vacuum oven at 100-120° C. and dried for 7-8 hours, then mixed with a perfluorinated solvent at a weight ratio of 1-20%:1, heated to 75-80° C., and stirred until completely dissolved to obtain an amorphous fluorinated copolymer solution; The amorphous fluorinated copolymer solution is finely filtered through a 10-15 μm filter into a liquid feed device of an injection device, and vacuum degassed at a constant temperature of 75° C. for standby use; S2. Mould surface treatment: Clean the silicon substrate mold in an ultrasonic cleaning machine to ensure that the substrate surface is free of dirt, then perform plasma treatment on the surface, spray a low-release fluorine coating, and bake in an oven at 120-150°C for 25-30 minutes; S3, Workstation preparation: Put the silicon-based substrate mold treated with S2 into the mold and place them together in a clean baking device to adjust the substrate level and clean the surface of the silicon-based substrate mold; after cleaning, start constant temperature heating at 60°C; S4, injection: Slowly open the baking equipment door, slowly extend the injection device to the top of the mold in the baking equipment and inject the material; After the injection is completed, the injection device is retracted and the ultrasonic device under the mold is turned on to assist leveling; S5. Baking: Set the temperature of the baking equipment to 120-150°C, maintain the vacuum state for 8-10 minutes, then start the solvent recovery device, stop the recovery after 2-3 minutes of air intake recovery, and maintain the vacuum state for 10-15 minutes again, and repeat this cycle until the solution is completely dry; S6, peeling: The silicon-based substrate mold with the dry film on the surface after S5 treatment is cooled to room temperature, and trimmed. The films on the four sides of the substrate are slowly peeled off with a trimming device until the films are completely peeled off; S7, Lamination: After the film is dusted, it is placed horizontally on the conveyor belt of the laminating device, and the laminating device is turned on to perform double-sided lamination protection on the film.

10. The method for preparing a perfluororesin film according to claim 9, characterized in that: Place In S1, the perfluorinated solvent is 3M-FC40 fluorinated liquid; In S2, the thickness of the low-release fluorine coating is 5 to 100 nm; In S4, the injection time is 3 to 15 seconds.

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