A method for preparing a medical perfluoroelastomer

Abstract

The application relates to the technical field of fluororubber, in particular to a preparation method of medical perfluororubber, and the medical perfluororubber is composed of components: fluororubber raw rubber, nanoscale filler, perfluoropolyether oil, vulcanizing agent antibacterial agent, fluorine wax powder, fluorinated graphene, potassium persulfate, ammonium perfluorooctanoate, pH buffer, oleic acid polyoxyethylene ester, 1,4-diiodoperfluorobutane, anhydrous calcium chloride and deionized water. The preparation method of the medical perfluororubber comprises the following steps: S1, polymerization; S2, condensation; S3, mixing; and S4, vulcanization. The mixing and vulcanization process are optimized, the prepared medical perfluororubber has excellent water vapor permeation resistance, antibacterial property and low cytotoxicity, the unification of high performance and biocompatibility of the perfluororubber is realized, and the medical perfluororubber is suitable for fields such as medical devices which have relatively high requirements on performance and safety.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of fluororubber, in particular to a preparation method of medical peroxide fluororubber. BACKGROUND

[0002] Peroxide fluororubber, also known as hexafluoropropylene (HFP) based fluororubber, has hexafluoropropylene (HFP) and vinylidene fluoride (VDF) as main chemical structural units. Compared with ordinary fluororubber, peroxide fluororubber has more excellent chemical resistance, heat resistance and mechanical properties, but the plasticity and flowability of peroxide fluororubber are poor, and it is difficult to uniformly disperse various compounding agents such as fillers, vulcanizing agents and accelerators in the mixing process, resulting in defects such as pores and depressions on the surface of the product, which affects the appearance and sealing performance of the product. SUMMARY

[0003] The application aims to provide a preparation method of medical peroxide fluororubber to solve the problems in the background.

[0004] To achieve the above-mentioned purpose, the application provides the following technical scheme: a preparation method of medical peroxide fluororubber, wherein the medical peroxide fluororubber is composed of the following components in parts by mass: 100 parts of fluororubber raw rubber, 10-20 parts of nanoscale filler, 5-8 parts of perfluoropolyether oil, 2-5 parts of vulcanizing agent, 1-3 parts of antibacterial agent, 1-2 parts of fluorine wax powder, 1-2 parts of fluorinated graphene, 0.5-1.5 parts of potassium persulfate, 0.5-1.0 parts of ammonium perfluorooctanoate, 0.5-1.0 parts of pH buffer, 0.3-0.8 parts of polyoxyethylene oleate, 0.2-0.5 parts of 1,4-diiodoperfluorobutane, 30-40 parts of anhydrous calcium chloride and 1800-2000 parts of deionized water.

[0005] The fluororubber raw rubber is composed of the following components in percentage by mass: 30-40% of vinylidene fluoride, 20-30% of hexafluoropropylene, 1-2% of perfluoromethyl vinyl ether and the balance of tetrafluoroethylene.

[0006] The preparation method of the medical peroxide fluororubber comprises the following steps:

[0007] S1, polymerization: adding ammonium perfluorooctanoate, pH buffer, polyoxyethylene oleate, 1,4-diiodoperfluorobutane and deionized water into a reaction kettle, replacing the air in the reaction kettle with nitrogen, stopping the nitrogen replacement when the pressure in the reaction kettle reaches 2.5-4.0 MPa, adding fluororubber raw rubber and potassium persulfate into the reaction kettle, heating to 55-80 DEG C, continuously stirring for 6-12 h, and cooling to room temperature to obtain a polymerization emulsion;

[0008] S2: coagulation: adding anhydrous calcium chloride to the polymerization emulsion, stirring thoroughly until no solid particles are precipitated, and sequentially filtering, washing with water and drying the solid particles to obtain raw perfluorinated rubber;

[0009] S3, mixing: adding raw perfluorinated rubber, nano-sized filler, vulcanizing agent, antibacterial agent, fluorine wax powder and fluorinated graphene into a mixer to mix, the mixing temperature is 120-150 DEG C, the mixing time is 10-20 min, to obtain a mixed rubber;

[0010] S4, vulcanization: placing the mixed rubber at room temperature for 24 h, and then vulcanizing and forming on a flat vulcanizing machine, the vulcanization temperature is 160-180 DEG C, the vulcanization time is 20-30 min, to obtain the medical perfluorinated rubber.

[0011] Optionally, the average particle size of the nano-sized filler is 30-100 nm, and the nano-sized filler is one or a combination of fumed silica and fluorinated carbon nanotube.

[0012] Optionally, the vulcanizing agent is one or a combination of two or more of triallyl isocyanurate, dicumyl peroxide, 1,3-bis (tert-butyl peroxide isopropyl) benzene.

[0013] Optionally, the antibacterial agent is one of fluorine-containing amphiphilic cationic antibacterial polymer PD45HF5, silver ion loaded zeolite and organosilicon quaternary ammonium salt antibacterial agent.

[0014] Optionally, the fluorinated graphene has a two-dimensional amorphous porous structure, the flake diameter of the fluorinated graphene is 4-10 mu m, and the fluorine content in the fluorinated graphene is 53-60%.

[0015] Optionally, the pH buffer is one of dipotassium hydrogen phosphate, potassium dihydrogen phosphate and disodium hydrogen phosphate.

[0016] Compared with the prior art, the present application has the following beneficial effects: the mixing and vulcanization process is optimized, the medical perfluorinated rubber prepared has excellent water vapor permeation resistance, antibacterial property and low cytotoxicity, the unification of high performance and biocompatibility of perfluorinated rubber is realized, and it is suitable for medical devices and other fields with high performance and safety requirements. BRIEF DESCRIPTION OF DRAWINGS

[0017] Figure 1 The cross-sectional scanning electron microscope image of the medical perfluorinated rubber prepared in Example 4. DETAILED DESCRIPTION

[0018] The technical solutions in the embodiments of the present application will be clearly and completely described below. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work fall within the protection scope of the present application.

[0019] Embodiment 1: The present application provides a preparation method of medical perfluororubber, the medical perfluororubber is composed of the following components by mass fraction: fluoroelastomer raw rubber 100 parts, nano filler 10 parts, perfluoropolyether oil 5 parts, vulcanizing agent 2 parts, antibacterial agent 1 part, fluorine wax powder 1 part, fluorinated graphene 1 part, potassium persulfate 0.5 part, ammonium perfluorooctanoate 0.5 part, pH buffer 0.5 part, polyoxyethylene oleate 0.3 part, 1,4-diiodoperfluorobutane 0.2 part, anhydrous calcium chloride 30 parts and deionized water 1800 parts;

[0020] The fluoroelastomer raw rubber is composed of the following components by mass percentage: vinylidene fluoride 30%, hexafluoropropylene 20%, perfluoromethyl vinyl ether 1%, and the balance is tetrafluoroethylene;

[0021] The preparation method of the medical perfluororubber comprises the following steps:

[0022] S1, polymerization: adding ammonium perfluorooctanoate, pH buffer, polyoxyethylene oleate, 1,4-diiodoperfluorobutane and deionized water into a reaction kettle, replacing the air in the reaction kettle with nitrogen, stopping the nitrogen inlet when the pressure in the reaction kettle reaches 2.5 MPa, adding fluoroelastomer raw rubber and potassium persulfate into the reaction kettle, heating to 55℃, continuously stirring for 6h, cooling to room temperature, and obtaining a polymerization emulsion;

[0023] S2, condensation: adding anhydrous calcium chloride into the polymerization emulsion, stirring thoroughly until no solid particles are precipitated, and sequentially filtering, washing with water and drying the solid particles to obtain perfluororubber raw rubber;

[0024] S3, mixing: adding the perfluororubber raw rubber, nano filler, vulcanizing agent, antibacterial agent, fluorine wax powder and fluorinated graphene into a banbury mixer for mixing, the mixing temperature is 120℃, and the mixing time is 10min, and a mixed rubber is obtained;

[0025] S4, vulcanization: placing the mixed rubber at room temperature for 24h, and then performing vulcanization molding on a flat plate vulcanization machine, the vulcanization temperature is 160℃, the vulcanization time is 20min, and the medical perfluororubber is obtained.

[0026] The application provides a medical peroxide fluororubber and a preparation method thereof.

[0027] The fluororubber raw rubber is composed of the following components in percentage by mass: vinylidene fluoride 35%, hexafluoropropylene 24%, perfluoromethyl vinyl ether 1%, and the balance being tetrafluoroethylene.

[0028] The preparation method of the medical peroxide fluororubber comprises the following steps:

[0029] S1, polymerization: adding ammonium perfluorooctanoate, pH buffer, polyoxyethylene oleate, 1,4-diiodoperfluorobutane and deionized water into a reaction kettle, replacing the air in the reaction kettle with nitrogen, stopping the nitrogen replacement when the pressure in the reaction kettle reaches 3.0 MPa, adding fluororubber raw rubber and potassium persulfate into the reaction kettle, heating to 60℃, continuously stirring for 8h, and cooling to room temperature to obtain a polymerization emulsion;

[0030] S2, condensation: adding anhydrous calcium chloride into the polymerization emulsion, fully stirring until no solid particles are precipitated, and sequentially filtering, washing with water and drying the solid particles to obtain peroxide fluororubber raw rubber;

[0031] S3, mixing: adding the peroxide fluororubber raw rubber, nanoscale filler, vulcanizing agent, antibacterial agent, fluorine wax powder and fluorinated graphene into a banbury mixer for mixing, the mixing temperature is 130℃, and the mixing time is 12min to obtain a mixed rubber;

[0032] S4, vulcanization: placing the mixed rubber at room temperature for 24h, and then performing vulcanization molding on a flat plate vulcanization machine, the vulcanization temperature is 170℃, and the vulcanization time is 25min to obtain the medical peroxide fluororubber.

[0033] The application provides a medical peroxide fluororubber and a preparation method thereof.

[0034] The fluororubber raw rubber is composed of the following components in mass percentage: vinylidene fluoride 35%, hexafluoropropylene 28%, perfluoromethyl vinyl ether 12%, and the balance being tetrafluoroethylene;

[0035] The preparation method of the medical perfluororubber comprises the following steps:

[0036] S1, polymerization: ammonium perfluorooctanoate, pH buffer, oleic acid polyoxyethylene ester, 1,4-diiodoperfluorobutane and deionized water are added into a reaction kettle, nitrogen is introduced to replace the air in the reaction kettle, when the pressure in the reaction kettle reaches 3.5 MPa, the nitrogen introduction is stopped, fluororubber raw rubber and potassium persulfate are added into the reaction kettle, the temperature is raised to 70℃, continuous stirring is carried out for 10h, and then the temperature is cooled to room temperature to obtain a polymerization emulsion;

[0037] S2, coagulation: anhydrous calcium chloride is added into the polymerization emulsion, and the mixture is fully stirred until no solid particles are precipitated, and then the solid particles are sequentially filtered, washed with water and dried to obtain perfluororubber raw rubber;

[0038] S3, mixing: the perfluororubber raw rubber, nano filler, vulcanizing agent, antibacterial agent, fluorine wax powder and fluorinated graphene are added into a mixing mill for mixing, the mixing temperature is 140℃, and the mixing time is 18min to obtain a mixed rubber;

[0039] S4, vulcanization: the mixed rubber is first placed at room temperature for 24h, and then vulcanized and formed on a flat plate vulcanizing machine, the vulcanization temperature is 175℃, the vulcanization time is 25min, and the medical perfluororubber is obtained.

[0040] In embodiment 4, the medical perfluororubber is prepared from the following components in mass parts: fluororubber raw rubber 100 parts, nano filler 20 parts, perfluoropolyether oil 8 parts, vulcanizing agent 5 parts, antibacterial agent 3 parts, fluorine wax powder 2 parts, fluorinated graphene 2 parts, potassium persulfate 1.5 parts, ammonium perfluorooctanoate 1.0 part, pH buffer 1.0 part, oleic acid polyoxyethylene ester 0.8 part, 1,4-diiodoperfluorobutane 0.5 part, anhydrous calcium chloride 40 parts and deionized water 2000 parts.

[0041] The fluororubber raw rubber is composed of the following components in mass percentage: vinylidene fluoride 40%, hexafluoropropylene 30%, perfluoromethyl vinyl ether 2%, and the balance being tetrafluoroethylene;

[0042] The preparation method of the medical perfluororubber comprises the following steps:

[0043] S1, polymerization: ammonium perfluorooctanoate, pH buffer, polyoxyethylene oleate, 1,4-diiodoperfluorobutane and deionized water were added into a reaction kettle, nitrogen was introduced to replace the air in the reaction kettle, when the pressure in the reaction kettle reached 4.0 MPa, the introduction of nitrogen was stopped, fluoroelastomer raw rubber and potassium persulfate were added into the reaction kettle, the temperature was raised to 80℃, continuous stirring for 12h, and then cooled to room temperature to obtain a polymerization emulsion;

[0044] S2, condensation: anhydrous calcium chloride was added into the polymerization emulsion, and stirred until no solid particles were precipitated, then the solid particles were sequentially filtered, washed with water and dried to obtain peroxide fluoroelastomer raw rubber;

[0045] S3, mixing: peroxide fluoroelastomer raw rubber, nano filler, vulcanizing agent, antibacterial agent, fluorine wax powder and fluorinated graphene were added into a mixing machine and mixed at a temperature of 150℃ for 20min to obtain a mixed rubber;

[0046] S4, vulcanization: the mixed rubber was first placed at room temperature for 24h, and then vulcanized and formed on a flat vulcanizing machine, the vulcanization temperature was 180℃, the vulcanization time was 30min, and the medical peroxide fluoroelastomer was obtained.

[0047] In examples 1-4, the average particle size of the nano filler was 30-100nm, the nano filler was a combination of fumed silica and fluorinated carbon nanotubes, and the mass ratio of fumed silica to fluorinated carbon nanotubes was 1:1. The fluorinated graphene was a two-dimensional amorphous porous structure, the flake diameter of the fluorinated graphene was 4-10μm, and the fluorine content in the fluorinated graphene was 53%-60%. The antibacterial agent was a fluorine-containing amphiphilic cationic antibacterial polymer PD45HF5.

[0048] In example 1, the vulcanizing agent was triallyl isocyanurate, and the pH buffer was dipotassium hydrogen phosphate. In example 2, the vulcanizing agent was dicumyl peroxide, and the pH buffer was dipotassium hydrogen phosphate. In example 2, the vulcanizing agent was 1,3-bis(tert-butyl peroxyisopropyl), and the pH buffer was monopotassium phosphate. In example 3, the vulcanizing agent was triallyl isocyanurate, and the pH buffer was disodium hydrogen phosphate. In example 4, the vulcanizing agent was dicumyl peroxide, and the pH buffer was disodium hydrogen phosphate.

[0049] Comparative example 1

[0050] The same as example 1, the only difference is that polyoxyethylene oleate, fluorine wax powder and fluorinated graphene are not used.

[0051] Test example 1

[0052] Test content: according to ASTM D412 and ASTM D624, the tensile strength and tear strength of the medical peroxide fluoroelastomer prepared in examples 1-4 and comparative example 1 were tested, and the specific results are shown in table 1.

[0053] Test Example 2

[0054] Test Content: The water vapor permeability, antibacterial rate (Staphylococcus aureus) and cytotoxicity of the medical perfluorinated rubber prepared in Examples 1-4 and Comparative Example 1 were tested according to ASTM E96, ISO 22196 and ISO 10993-5, respectively, and the specific results are shown in Table 1.

[0055] Table 1

[0056]

[0057] As can be seen from Table 1, the tensile strength and tear strength of the medical perfluorinated rubber prepared in Examples 1-4 are significantly better than those of the medical perfluorinated rubber prepared in Comparative Example 1, among which the perfluorinated rubber prepared in Example 4 performs best and is worth popularizing.

[0058] The perfluorinated rubber prepared in Example 4 was cut along its cross section, and scanning electron microscopy showed that there were no obvious pores, depressions or other defects in the cross section. Therefore, the perfluorinated rubber raw rubber can be uniformly dispersed with various additives during the mixing process.

[0059] Although embodiments of the present application have been shown and described, it is to be understood that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the application, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A method for preparing medical-grade peroxyfluororubber, characterized in that: The medical-grade peroxyfluororubber is prepared from the following components in parts by weight: 100 parts of fluororubber raw rubber monomer, 10-20 parts of nano-grade filler, 5-8 parts of perfluoropolyether oil, 2-5 parts of vulcanizing agent, 1-3 parts of antibacterial agent, 1-2 parts of fluorowax powder, 1-2 parts of fluorinated graphene, 0.5-1.5 parts of potassium persulfate, 0.5-1.0 parts of perfluorooctanoic acid ammonium, 0.5-1.0 parts of pH buffer, 0.3-0.8 parts of oleic acid polyoxyethylene ester, 0.2-0.5 parts of 1,4-diiodoperfluorobutane, 30-40 parts of anhydrous calcium chloride, and 1800-2000 parts of deionized water; The fluororubber raw rubber monomer is composed of the following components by mass percentage: 30%–40% vinylidene fluoride, 20%–30% hexafluoropropylene, 1%–2% perfluoromethyl vinyl ether, and the balance being tetrafluoroethylene. The preparation method of the medical-grade peroxyfluororubber includes the following steps: S1. Polymerization: Add ammonium perfluorooctanoate, pH buffer, polyoxyethylene oleate, 1,4-diiodoperfluorobutane and deionized water to the reactor. Purge nitrogen gas to displace the air in the reactor. Stop purging nitrogen gas when the pressure in the reactor reaches 2.5-4.0 MPa. Add fluororubber raw rubber monomer and potassium persulfate to the reactor. Heat to 55-80℃ and stir continuously for 6-12 hours. Cool to room temperature to obtain the polymer emulsion. S2: Coagulation: Add anhydrous calcium chloride to the polymer emulsion and stir thoroughly until no solid particles precipitate. Filter, wash and dry the solid particles in sequence to obtain peroxyfluororubber raw rubber. S3. Mixing: Add the peroxyfluorinated rubber raw rubber, nano-grade filler, vulcanizing agent, antibacterial agent, fluorinated wax powder and fluorinated graphene into a mixer and mix them. The mixing temperature is 120-150℃ and the mixing time is 10-20 minutes to obtain the mixed rubber. S4. Vulcanization: The compound rubber is left to stand at room temperature for 24 hours, and then vulcanized on a flat vulcanizing machine. The vulcanization temperature is 160-180℃ and the vulcanization time is 20-30 minutes to obtain the medical peroxyfluorinated rubber.

2. The method for preparing medical-grade peroxyfluororubber according to claim 1, characterized in that: The average particle size of the nanoscale filler is 30-100 nm, and the nanoscale filler is one or a combination of fumed silica and fluorinated carbon nanotubes.

3. The method for preparing medical-grade peroxyfluororubber according to claim 1, characterized in that: The vulcanizing agent is a peroxide, or a combination of a peroxide and triallyl isocyanurate, wherein the peroxide is selected from one or two of dicumyl peroxide and 1,3-bis(tert-butylperoxyisopropyl)benzene.

4. The method for preparing medical-grade peroxyfluororubber according to claim 1, characterized in that: The antibacterial agent is one of the following: fluorine-containing amphiphilic cationic antibacterial polymer PD45HF5, silver ion-supported zeolite, or organosilicon quaternary ammonium salt antibacterial agent.

5. The method for preparing medical-grade peroxyfluororubber according to claim 1, characterized in that: The fluorinated graphene has a two-dimensional amorphous porous structure, the sheet diameter of the fluorinated graphene is 4-10 μm, and the fluorine content in the fluorinated graphene is 53%-60%.

6. The method for preparing medical-grade peroxyfluororubber according to claim 1, characterized in that: The pH buffer is one of dipotassium hydrogen phosphate, potassium dihydrogen phosphate, and disodium hydrogen phosphate.

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