CN111548522A - Device for plasma-initiated surface graft polymerization modification of polymer material - Google Patents

Abstract

The present invention relates to the technical field of surface graft polymerization devices, in particular to a device for plasma-induced surface graft polymerization modification of polymer materials, comprising a plasma generator, wherein the plasma generator has a built-in reaction vessel, The polymer material used for surface graft polymerization is placed in the reaction container, and the mouth of the reaction container is provided with a two-way straight piston, which is respectively connected with the monomer solution oxygen removal system and the monomer solution through the two-port connecting pipe A. A non-polymerizable gas supply system is connected, the monomer solution deaeration system is used for supplying the reaction monomer solution into the reaction vessel, and the non-polymerizable gas supply system is used for supplying the plasma-treated non-polymeric gas into the reaction vessel. gas. The device is convenient to build and operate, and effectively solves the problem that the reaction cannot effectively remove oxygen, and ensures the smooth progress of the graft polymerization reaction.

Description

Device for Plasma-Initiated Surface Grafting Polymerization Modification of Polymer Materials

technical field

The invention relates to the technical field of surface graft polymerization devices, in particular to a device for plasma-induced surface graft polymerization modification of polymer materials.

Background technique

Surface grafting is an important method for surface modification of polymer materials, which can effectively improve the surface properties of materials, such as hydrophilicity, pollution resistance, adhesion and wear resistance. Among many surface graft modification methods, plasma-induced graft polymerization modification is a method that has developed rapidly in recent years, which does not affect the bulk properties of the material, and has the characteristics of high efficiency, low cost, and environmental protection. In the plasma-induced graft polymerization experiment, the surface of the material is first treated with a non-polymeric gas plasma under a certain degree of vacuum to generate active species such as free radicals on the surface; then contact with the pre-deoxygenated olefinic monomer solution ; Finally, the surface graft polymerization reaction is carried out under certain conditions, and the entire operation process requires strict sealing conditions. In order to ensure the tightness of the experimental device, the existing technology can only integrate the devices of the above-mentioned three links of "plasma surface treatment", "preliminary deoxygenation of monomer solution" and "surface graft polymerization". disassemble. The "surface graft polymerization reaction" link needs to be carried out under the avoidance of oxygen and the set reaction temperature, time, and stirring. The control of the reaction temperature and stirring conditions requires separate auxiliary equipment (such as temperature control instruments, magnetic stirrers, etc. ). Obviously, it is very inconvenient and difficult to build and connect the complex device of the above three links with the auxiliary equipment, and the reaction is not easy to control.

In addition, due to the small number of active species such as free radicals generated by plasma, the reaction process must strictly avoid oxygen. However, using the traditional "inert gas flooding method", it is difficult to remove the trace oxygen dissolved in the monomer solution, which is easy to cause grafting. Polymerization failed. Therefore, based on the above analysis, it is necessary to develop a new plasma-induced graft polymerization device that is easy to operate and can effectively avoid oxygen.

SUMMARY OF THE INVENTION

The purpose of the present invention is to provide a device for plasma-induced surface graft polymerization modification of polymer materials, which is convenient to build and operate, and can effectively solve the problem that the reaction cannot effectively remove oxygen.

The technical scheme of the present invention is as follows: a device for plasma-induced surface graft polymerization modification of polymer materials, comprising a plasma generator, wherein a reaction container is placed inside the plasma generator, and a reaction container is placed in the reaction container There is a polymer material for surface graft polymerization, and the mouth of the reaction vessel is provided with a two-way straight-way piston, and the two-way straight-way piston is respectively connected with the monomer solution oxygen removal system and the non-polymeric gas supply system through the two-port connecting pipe A. In connection, the monomer solution oxygen removal system is used for supplying the reaction monomer solution into the reaction vessel, and the non-polymerizable gas supply system is used for supplying the plasma-treated non-polymerizable gas into the reaction vessel.

Further, the monomer solution deoxygenation system includes a spherical separatory funnel with a built-in reaction monomer solution, and the lower opening of the spherical separatory funnel is provided with a piston for switching and an opening on the upper part of the two-port connecting pipe A. Connected, the upper mouth of the spherical separatory funnel is connected with the lower mouth of the two-port connecting pipe B, and the two openings on the upper part of the two-port connecting pipe B are respectively connected with the glass capillary and the U-shaped oil seal. One end is connected to an inert gas source, and the other end of the glass capillary goes through the two-port connecting pipe B and extends into the spherical separatory funnel. The bottom of the glass capillary is completely immersed in the reaction monomer solution.

Further, the glass capillary tube includes an air inlet part, a standard grinding plug, a reducing part and a small diameter part in order from top to bottom; the air inlet part is connected with an inert gas source; the standard grinding plug is connected with a two-port connecting pipe An opening on the upper part of B is connected; the diameter-reducing part is located inside the two-port connecting pipe B and the spherical separatory funnel; the narrow-diameter part is set below the liquid level of the reaction monomer solution.

Further, the length of the thin-diameter part is 1-3 cm, and the inner diameter of the end of the thin-diameter part is 0.1-0.5 mm.

Further, a valve is provided between the air inlet and the inert gas source.

Further, the U-shaped oil seal includes a U-shaped glass tube, a rubber plug and a silicone oil arranged in the U-shaped glass tube, and the two sides of the U-shaped glass tube are symmetrically provided with an air inlet and an air outlet; the air inlet It is connected with another opening on the upper part of the two-port connecting pipe B, and the air outlet communicates with the atmosphere.

Further, the non-polymeric gas supply system includes a vacuum oil pump connected to another opening on the upper part of the two-port connecting pipe A through a rubber tube, and a non-polymeric gas inlet and a vacuum gauge are respectively provided on the rubber tube, The non-polymeric gas inlet is connected to an external non-polymeric gas source.

Further, a magnetic stirring bar for stirring is arranged in the reaction container, and a magnet for adsorbing and fixing the magnetic stirring bar near the mouth of the reaction container is fixed on the outer wall of the reaction container through a rubber band.

Further, the polymer material is polyethylene, polypropylene or polyvinylidene fluoride.

Compared with the prior art, the present invention has the following advantages:

1. The device of the present invention is provided with a unique two-way straight path piston between the reaction vessel, the non-polymerizable gas supply system and the monomer solution oxygen removal system, and the reaction vessel and the two-way straight path piston can be disassembled as a whole during the graft polymerization. , the reaction was carried out under the set conditions alone. Compared with the existing plasma-induced graft polymerization device that cannot be disassembled, the experimental operation of the device of the present invention is very convenient and simple.

2. The deoxygenation system of the monomer solution of the device of the present invention uses a glass capillary to blow inert gas into the monomer liquid to deoxygenate. Compared with the existing traditional "inert gas flooding method", the present invention can effectively remove the reaction The trace amount of oxygen dissolved in the monomer liquid is conducive to the smooth progress of the subsequent graft polymerization.

3. There is a U-shaped oil seal in the monomer solution deoxidizing system of the device of the present invention, which can be used to discharge the inert gas blown into the system, and isolate the outside oxygen from "sucking back" into the deoxidizing system, and it can also be used intuitively and conveniently. The size of the inert gas bubbling flow rate in the system can be judged.

4. The device of the present invention is provided with a valve between the inlet part of the glass capillary tube and the inert gas source, through which the flow rate of the inert gas can be easily adjusted, which is conducive to saving inert gas and reducing costs.

5. The device of the present invention is fixed with a magnet on the upper end of the outer wall of the reaction vessel, which can effectively avoid side reactions due to the presence of a magnetic stirrer during plasma treatment.

Description of drawings

Figure 1 is a schematic diagram of the overall structure of the present invention.

Figure 2 is a schematic view of the structure of the glass capillary of the present invention.

FIG. 3 is a schematic structural diagram of the U-shaped oil seal of the present invention.

FIG. 4 is a partial enlarged view of part C in FIG. 1 of the present invention.

In the figure: 1-Reaction vessel, 4-Two-port connecting pipe A, 5-Plasma generator, 6-Two-way straight piston, 7-Magnetic stirring bar, 8-Magnet, 11-Polymer material, 21-Spherical separator Liquid funnel, 22-glass capillary, 23-two-port connecting pipe B, 24-U type oil seal, 25-valve, 31-vacuum oil pump, 32-non-polymer gas inlet, 33-vacuum gauge, 221-air inlet , 222-standard grinding plug, 223-reducing part, 224-small diameter part, 241-U-shaped glass tube, 242-rubber plug, 243-silicone oil, 244-air inlet, 245-air outlet.

Detailed ways

In order to make the above-mentioned features and advantages of the present invention easier to understand, the following specific embodiments are given and the accompanying drawings are described in detail as follows, but the present invention is not limited thereto.

Refer to Figures 1 to 4

A device for plasma-initiated graft polymerization modification on the surface of a polymer material includes a plasma generator 5, and the plasma generator has a built-in reaction vessel 1, and the reaction vessel preferably adopts a test tube with a grinding mouth. The polymer material 11 for surface graft polymerization is placed in the reaction vessel, and the mouth of the reaction vessel is provided with a two-way straight-way piston 6, which is deoxygenated from the monomer solution through the two-port connecting pipe A4 respectively. The system is connected to a non-polymerizable gas supply system, the monomer solution deaeration system is used to supply the reaction monomer solution into the reaction vessel, and the non-polymerizable gas supply system is used to supply the plasma-treated non-polymer into the reaction vessel. polymerizable gas. After the non-polymerizable gas supply system supplies the non-polymerizable gas to the reaction vessel 1, the reaction vessel 1 is placed in the plasma generator 5, and the plasma generator 5 energizes the polymer at the bottom of the reaction vessel 1. The surface of the material 11 is subjected to plasma treatment. After the treatment, open the oxygen removal system of the monomer solution, so that the reaction monomer solution enters the reaction container 1 and contacts the surface of the polymer material 11, then closes the two-way straight-way piston 6, and disassembles the reaction container 1 and the two-way straight-way piston 6 as a whole Next, the surface graft polymerization was carried out under the set conditions.

Obviously, the two-way straight piston set here can make the experimental operation very convenient and simple. This is because the disassembled reaction vessel and the two-way straight-way piston device are simple in composition, small in size, and easy to move. It is very convenient to operate when connecting it with auxiliary equipment for controlling reaction conditions (such as temperature control instruments, magnetic stirrers, etc.). The reaction is also easy to control. However, the device in the prior art cannot be disassembled, and it is quite inconvenient and difficult to operate when it is connected with the reaction auxiliary equipment. In addition, the two-way straight piston adopts a combined design of grinding mouth and grinding plug, which can ensure the sealing of the whole system when it is connected with the glass instruments in the upper and lower parts.

In this embodiment, the monomer solution deoxygenation system includes a spherical separatory funnel 21 with a built-in reaction monomer solution, the lower port of the spherical separatory funnel is provided with a piston 211 for opening and closing, and is connected to the two-port connecting pipe A4 One opening on the upper part is connected, the upper opening of the spherical separatory funnel is connected with the lower opening of the two-port connecting pipe B23, and the two openings on the upper part of the two-port connecting pipe B are respectively connected with the glass capillary 22 and the U-shaped oil seal 24. , one end of the glass capillary is connected to an inert gas source, and the inert gas source is preferably argon. The other end of the glass capillary passes through the two-port connecting pipe B and extends into the interior of the spherical separatory funnel. The bottom of the glass capillary is completely immersed in the reaction monomer solution, and the inert gas provided by the inert gas source is blown into the reaction monomer solution. . At this time, the inert gas will form a large number of bubbles in the monomer solution and be discharged. This process will cause a violent disturbance to the solution, and then the dissolved oxygen in the solution can be completely resolved to achieve the effect of deep deoxygenation.

In this embodiment, the glass capillary tube includes an air inlet portion 221, a standard mill plug 222, a variable diameter portion 223 and a narrow diameter portion 224 in sequence from top to bottom; the air inlet portion is connected to an inert gas source; the standard mill The plug is connected to an opening on the upper part of the two-port connecting pipe B; the variable diameter part is located inside the two-port connecting pipe B and the spherical separatory funnel; the thin-diameter part is arranged below the liquid level of the reaction monomer solution. Wherein, the length of the narrow portion is 1 to 3 cm, and the inner diameter of the end of the narrow portion is 0.1 to 0.5 mm. Preferably, the length of the small diameter portion 224 is 2 cm, and the inner diameter of the tip is 0.3 mm.

In this embodiment, a valve 25 is provided between the air inlet and the inert gas source. The flow rate of the inert gas can be easily adjusted through the valve. When the inert gas is first inflated, due to the presence of a large amount of oxygen in the system, the valve needs to be enlarged at this time, and a large amount of inert gas is inflated to drive out the oxygen; and after the gas is inflated for a period of time, its flow rate can be greatly reduced by adjusting the valve. Keep the pressure in the system higher than the external pressure. Therefore, the setting of the valve is beneficial to save the inert gas and reduce the cost.

In this embodiment, the U-shaped oil seal 24 includes a U-shaped glass tube 241, a rubber plug 242, and a silicone oil 243 disposed in the U-shaped glass tube. The U-shaped glass tube is symmetrically provided with an air inlet 244 and an outlet on both sides. Air port 245; the air inlet is connected to another opening on the upper part of the two-port connecting pipe B, and the air outlet communicates with the atmosphere. The U-shaped oil seal can be used to discharge the inert gas blown into the system, and by observing the reciprocating flow of the silicone oil in the U-shaped oil seal, the flow rate of the inert gas blown into the glass capillary in the system can be intuitively and conveniently determined. In order to adjust the inert gas The drum speed provides a reference basis. In addition, the U-shaped oil seal can also isolate the outside oxygen from "sucking back" into the deoxygenation system.

In this embodiment, the non-polymeric gas supply system includes a vacuum oil pump 31 connected to the other opening on the upper part of the two-port connecting pipe A through a rubber tube, and the non-polymeric gas inlets 32 are respectively provided on the rubber tubes. and a vacuum gauge 33, the non-polymeric gas inlet is connected to a non-polymeric gas source. The inside of the reaction vessel 1 is evacuated by the vacuum oil pump 31 , and then the non-polymerizable gas is charged through the non-polymerizable gas inlet port 32 .

Preferably, the vacuum gauge is a Maxwell vacuum gauge, the non-polymeric gas source is argon gas, the reaction vessel 1 is evacuated to 1 Pa through the vacuum oil pump 31, and then filled with argon gas through the non-polymeric gas inlet port 32, repeating several times First, to ensure that the reaction vessel 1 is in an argon atmosphere, and then pumped through the vacuum oil pump 31 to a vacuum pressure of 10 Pa in the reaction vessel 1 .

In this embodiment, the reaction vessel is provided with a magnetic stirrer 7 for stirring, and the outer wall of the reaction vessel 1 is fixed with a magnet 8 through a rubber band. The magnet 8 is used to adsorb and fix the magnetic stirrer 7 on the reaction vessel 1 near the mouth. By arranging the magnet 8, side reactions due to the presence of the magnetic stirrer during plasma treatment can be effectively avoided. This is because the arrangement of the magnet 8 can completely isolate the magnetic stirring bar 7 from the polymer material 11 to be processed (located at the bottom of the lower end of the reaction vessel). When the plasma treatment is performed, the glow discharge is mainly concentrated in the area of the polymer material 11 at the lower end of the reaction vessel, and the surface of the magnetic stirrer 7 will not be subjected to plasma treatment to generate active species, so that the surface of the polymer material 11 will not be subjected to subsequent plasma treatment. The graft polymerization reaction produces hindered interference. When the polymer material 11 is in contact with the monomer solution for graft polymerization, the magnet 8 can be removed, and the magnetic stirrer 7 can enter the monomer solution to ensure that the reaction proceeds under stirring conditions.

In this embodiment, the polymer material is polyethylene, polypropylene or polyvinylidene fluoride.

In this embodiment, all the glass instruments are connected by a combination of standard grinding mouth and standard grinding plug, and vacuum silicone ester is coated on the surface of the standard grinding plug to improve the gas tightness.

Concrete experimental process of the present invention:

Take poly(polyethylene glycol methacrylate) graft modified polypropylene porous membrane as an example. Add 15 mL of an aqueous solution of polyethylene glycol methacrylate monomer (concentration of 0.3 mol/L) to a spherical separatory funnel, and place the acetone pre-washed polypropylene porous membrane (length 6 cm) into the test tube of the reaction vessel , and then set up the experimental device as shown in Figure 1. After 30min of deoxygenation of the monomer solution by bubbling argon gas through the glass capillary, the vacuum oil pump was turned on, the test tube was evacuated to 1Pa, and then argon gas was filled through the argon gas inlet, and repeated several times to ensure that the test tube was filled with argon gas Atmosphere, re-evacuated to 10Pa. The test tube was placed in a plasma generator, and the surface of the polypropylene porous membrane was treated for 5 min under the condition of a power of 3 W, and the test tube was continuously rotated to make the treatment uniform. Then open the piston of the spherical separatory funnel to let the monomer solution enter the test tube and contact the surface of the porous membrane, then close the two-way straight piston, remove the test tube and the two-way straight piston as a whole (remove the magnet at the same time), at 40 ℃ 20h of graft polymerization under stirring conditions. After the reaction was completed, the film was taken out and washed with water for more than 48 hours to remove unreacted monomers and possible poly(polyethylene glycol methacrylate) homopolymers.

The above are only preferred embodiments of the present invention. For those of ordinary skill in the art, according to the teachings of the present invention, different forms of devices for plasma-induced surface graft polymerization modification of polymer materials can be designed No creative work is required, and all equivalent changes, modifications, substitutions and alterations made according to the scope of the patent application of the present invention without departing from the principle and spirit of the present invention shall fall within the scope of the present invention.

Claims (9)

1. a device for plasma-induced surface graft polymerization modification of polymer material, is characterized in that, comprises plasma generator, and described plasma generator is built-in with reaction vessel, and in described reaction vessel, is placed useful On the surface-grafted polymer material, the mouth of the reaction vessel is provided with a two-way straight-way piston, and the two-way straight-way piston is respectively connected to the monomer solution oxygen removal system and the non-polymeric gas supply system through the two-port connecting pipe A. In connection, the monomer solution oxygen removal system is used for supplying the reaction monomer solution into the reaction vessel, and the non-polymerizable gas supply system is used for supplying the plasma-treated non-polymerizable gas into the reaction vessel. 2 . The device for plasma-induced surface graft polymerization modification of polymer materials according to claim 1 , wherein the monomer solution oxygen removal system comprises a spherical separatory funnel with a built-in reaction monomer solution. 3 . , the lower port of the spherical separatory funnel is provided with a piston for switching and is connected with an opening on the upper part of the two-port connecting pipe A, and the upper port of the spherical separatory funnel is connected with the lower port of the two-port connecting pipe B, so The two openings on the upper part of the two-port connecting pipe B are respectively connected with a glass capillary and a U-shaped oil seal. One end of the glass capillary is connected to an inert gas source, and the other end of the glass capillary passes through the two-port connecting pipe B and extends into the spherical part. Inside the liquid funnel, the bottom of the glass capillary is completely immersed in the reaction monomer solution. 3 . The device for plasma-induced graft polymerization modification of polymer material surface according to claim 2 , wherein the glass capillary tube comprises an air inlet, a standard grinding plug, a variable diameter in sequence from top to bottom. 4 . The air inlet part is connected with the inert gas source; the standard grinding plug is connected with an opening on the upper part of the two-port connecting pipe B; the reducing part is located in the two-port connecting pipe B and the spherical separatory funnel Inside; the small diameter portion is provided below the liquid level of the reaction monomer solution. 4 . The device for plasma-initiated graft polymerization modification of polymer material according to claim 3 , wherein the length of the thin-diameter part is 1-3 cm, and the inner diameter of the end of the thin-diameter part is 0.1 cm 4 . ~0.5mm. 5 . The device for plasma-initiated graft polymerization modification on the surface of polymer materials according to claim 3 , wherein a valve is provided between the air inlet and the inert gas source. 6 . 6. The device for plasma-initiated graft polymerization modification of polymer material according to claim 2, 3, 4 or 5, wherein the U-shaped oil seal comprises a U-shaped glass tube, a rubber stopper and Silicone oil arranged in a U-shaped glass tube, the two sides of the U-shaped glass tube are symmetrically provided with an air inlet and an air outlet; the air inlet is connected to another opening on the upper part of the second-port connecting pipe B, and the air outlet is Connect to the atmosphere. 7. The device for plasma-initiated graft polymerization modification of polymer materials according to claim 1, 2, 3, 4 or 5, wherein the non-polymeric gas supply system comprises a rubber tube For the vacuum oil pump connected to the other opening on the upper part of the two-port connecting pipe A, a non-polymeric gas inlet and a vacuum gauge are respectively provided on the rubber tube, and the non-polymeric gas inlet is externally connected to a non-polymeric gas source. 8. The device for plasma-induced surface graft polymerization modification of polymer materials according to claim 1, wherein the reaction vessel is provided with a magnetic stirrer for stirring, and the outer wall of the reaction vessel is provided with a rubber band. A magnet for attracting and fixing the magnetic stirrer to the vicinity of the mouth of the reaction vessel is fixed. 9 . The device for plasma-initiated graft polymerization modification on the surface of a polymer material according to claim 1 , wherein the polymer material is polyethylene, polypropylene or polyvinylidene fluoride. 10 .

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