CN101935821B - Preparation method of polymaleic anhydride film - Google Patents
Preparation method of polymaleic anhydride film Download PDFInfo
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- CN101935821B CN101935821B CN 201010517374 CN201010517374A CN101935821B CN 101935821 B CN101935821 B CN 101935821B CN 201010517374 CN201010517374 CN 201010517374 CN 201010517374 A CN201010517374 A CN 201010517374A CN 101935821 B CN101935821 B CN 101935821B
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Abstract
The invention discloses a preparation method of a polymaleic anhydride film, comprising the following steps of: placing a certain amount of maleic anhydride and a film-plating substrate slide into a plasma deposition furnace; after vacuumizing a background to 2.0*10<-3> Pa, heating by 50-200 DEG C, regulating chamber pressure to be 0-50Pa, discharging for 5-30minutes under the power of 5-30w, and plating a uniform polymaleic anhydride film layer on the slide. By the cooperation of maleic anhydride solid sublimation and plasma polymerization, the invention simplifies the preparation process of the polymaleic anhydride film; the prepared film has even and compact structure, the thickness of the film and the retention rate of a surface anhydride group are controllable, namely that the obtained polymaleic anhydride film has even structure, the content of the surface anhydride group can be controlled in a range of 5.59*10-8-2.11*10-7mol/cm2, and the thickness of the film can be controlled in a range of 110-661nm.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to utilize the standby a kind of performance of the distillation of solid maleic anhydride monomer raw material and plasma activated chemical vapour deposition coordinate system and the controlled polymaleic anhydride film of thickness.
Background technology
Polymaleic anhydride is because containing a large amount of carboxylic acid anhydride substituting groups on the main chain, structure is special, and excellent performance is a kind of broad-spectrum functional polymer compound.Utilize the maleic anhydride monomer autohemagglutination or can prepare the different polymaleic anhydride film of properity with other monomer copolymerization.By the polymaleic anhydride plated film, can introduce polar functional group at material surface.Yet traditional polymaleic anhydride film preparation method complex steps, cost are high, environmental-protecting performance is poor.Plasma Polymerization is a kind of new technology of deposition polymeric membrane.At present, the application Plasma Polymerization prepares polymaleic anhydride film and mainly contains dual mode, and plasma body causes maleic anhydride polymerization and maleic anhydride plasma polymerization.The former adopts argon or oxygen plasma activation substrate and substrate, causes the maleic anhydride monomer polymerization film formation.The latter is to the direct discharge generation maleic anhydride of maleic anhydride monomer plasma polymerization film forming.Correlative study shows that plasma body causes maleic anhydride polymerisate anhydride group and can finely preserve, but polymerization yield rate is very low; A large amount of anhydride groups are destroyed in the maleic anhydride plasma polymerization process falls, and is difficult to the reservation amount of control anhydride group.In addition, these two kinds of methods all need to introduce the gaseous state maleic anhydride monomer in plasma chamber, (wherein the gaseous state maleic anhydride can obtain by the distillation of maleic anhydride solid and the vaporization of maleic anhydride solution), the acquisition of the outer gas of cavity and gas are introduced needs to consume extra energy on the one hand, also make on the other hand experimental installation complicated, the experimental implementation difficultyization.Simultaneously, the gained film thickness also is difficult to control.Therefore, it is significant to utilize the plasma polymerization technology to develop the preparation method of the controlled polymaleic anhydride film of a kind of simple, economy, environmental protection, anhydride group retention rate, thickness.
Summary of the invention
The present invention will solve above-mentioned technical problem and propose a kind of in plasma chamber directly in the sublimation solid maleic anhydride, it is carried out the preparation method that glow discharge prepares polymaleic anhydride film, thereby so that anhydride group retention rate, thickness are controlled, and the simplification experimental installation is oversimplified experimental implementation.
Know-why of the present invention
The present invention is that the heating system of utilizing the plasma enhanced chemical vapor deposition stove to carry makes the directly distillation in cavity of maleic anhydride solid in principle, and simultaneously plasma discharging polymerization is with the controlled polymaleic anhydride film of preparation properity.
Technical scheme of the present invention
The present invention is heating sublimation solid maleic anhydride monomer in plasma-deposited stove, adopt lower temperature plasma technology, utilize glow discharge the plasma of gaseous state maleic anhydride monomer, make it produce living radical, between these living radicals or between free radical and the monomer polyaddition reaction occurs and form polymeric film.The solid maleic anhydride is at the plasma reaction chamber discharge polymerisation that directly distils, avoided adding at plasma-deposited stove the pipeline that transports of maleic anhydride gasification installation and gasification monomer thereof, economize the energy, nuisanceless, satisfy the needs of energy-conservation and environmental protection and conversion unit is required low, experimental implementation is oversimplified; In addition, literization and polymerization synergistic carry out making the output of polymkeric substance to increase substantially.Can be undertaken by following operation for obtaining the controlled polymaleic anhydride film of properity, maleic anhydride and film plating substrate are placed in the plasma-deposited stove, take out base vacuum to 2.0 * 10
-3Behind the Pa, be heated to certain temperature, regulate chamber pressure, under certain power, can plate the uniform film of one deck at slide glass behind the discharge certain hour.In this preparation system, can control by controlling the processing parameters such as Heating temperature and speed, discharge pressure, power, time, temperature structure and the character of polymeric membrane.
A kind of preparation method of polymaleic anhydride film specifically mainly comprises the following steps:
(1), take by weighing pulverous maleic anhydride monomer raw material with weighing bottle, this weighing bottle is fixed in the center of culture dish, again slide glass is fixed in this culture dish, make its be dispersed in weighing bottle around;
(2), step (1) gained system is placed plasma-deposited stove, take out base vacuum to 2.0 * 10
-3Behind the Pa,
Heat up 60～150 ℃, regulate chamber pressure 0～50Pa, under the power of 5～30w, discharge 5～30min can plate the even polymaleic anhydride film product of one deck at slide glass.
The heating installation that carries in the described plasma-deposited stove solid maleic anhydride monomer raw material is directly distilled, and the plasma aggregation deposition becomes film.
The polymaleic anhydride film even structure of above-mentioned preparation method's gained of the present invention, surface acid anhydride group content can be controlled in 5.59 * 10
-8～2.11 * 10
-7Mol/cm
2In the scope; Film thickness can be controlled in 110～661nm scope.
Technique effect of the present invention
The preparation method of a kind of polymaleic anhydride film of the present invention namely passes through maleic anhydride directly distillation, plasma body polymerization film formation in plasma reaction chamber.The solid maleic anhydride is at the plasma reaction chamber discharge polymerisation that directly distils, avoided adding at plasma-deposited stove the pipeline that transports of maleic anhydride gasification installation and gasification monomer thereof, economize the energy, nuisanceless, satisfy the needs of energy-conservation and environmental protection and conversion unit is required low, experimental implementation is oversimplified; In addition, literization and polymerization synergistic carry out making the output of polymkeric substance to increase substantially.Simultaneously preparation method of the present invention has simple to operately, and it is convenient to process, and is easy to industrialization, for the controlled preparation of polymaleic anhydride film provides new approach.The retention rate of the thickness of gained polymaleic anhydride film of the present invention, surface acid anhydride group is all controlled, and anhydride group content can be controlled in 5.59 * 10
-8～2.11 * 10
-7Mol/cm
2In the scope, film thickness can be controlled in 110～661nm scope.
Description of drawings
The stereoscan photograph of the product of Fig. 1, embodiments of the invention 1;
The infrared spectrogram of the product of Fig. 2, embodiments of the invention 1.
Embodiment
Also the present invention is further described by reference to the accompanying drawings below by embodiment, but do not limit the present invention.
Embodiment 1
(1) weighing bottle with 25 mm * 25 mm takes by weighing the pulverous maleic anhydride of 3.0 g, this weighing bottle is placed the center of 90 mm culture dish, slide glass with four 1 mm * 2.5 mm is fixed in this culture dish again, make its be dispersed in weighing bottle around;
(2) step (1) gained system is placed plasma-deposited stove, take out base vacuum to 2.0 * 10
-3Behind the Pa, be warming up to 100 ℃, the control chamber chamber pressure is between 20-30Pa, and under the power of 10w, discharge 10min can plate the uniform film of one deck at slide glass, obtains product of the present invention.
With a scanning electronic microscope (launch environment scanning electron microscope (FEI QUANTA FEG), PHILIPS Co.'s product), fourier transform infrared spectroscopy ((NEXUS870), U.S. Nicolet company produces) characterizes pattern, structure and the thickness of film.
With toluidine blue reagent and ultraviolet spectrophotometer ((UV-1800) Japanese SHIMADZU company product) film surface anhydride group content is measured.
SEM photo such as Fig. 1 of polymaleic anhydride film can find out obviously that this film thickness is even, compact structure, and smooth surface is smooth.Fig. 2 (b) is the polymaleic anhydride film infrared spectrogram, and the complex structure of this polymkeric substance contrasts maleic anhydride monomer (Fig. 2 (a)), 1780 and 1860 cm as seen from the figure
-1The carbonylic stretching vibration peak still exists in the corresponding acid anhydrides, but absorption intensity obviously dies down, and this is because the part anhydride group has fallen in that the plasma process is destroyed.The mean thickness of gained film is that 534 nm, anhydride group content are 2.11 * 10
-7Mol/cm
2
Embodiment 2
In the step (2), be warming up to and change 60 ℃ into, other conditions and step and embodiment 1 are identical.The mean thickness of gained film is that 249nm, anhydride group content are 9.91 * 10
-8Mol/cm
2
Embodiment 3
In the step (2), be warming up to and change 150 ℃ into, other conditions and step and embodiment 1 are identical.The mean thickness of gained film is that 228nm, anhydride group content are 8.30 * 10
-8Mol/cm
2
Embodiment 4
In the step (2), discharge power changes 5w into, and other conditions and step and embodiment 1 are identical.The mean thickness of gained film is that 265nm, anhydride group content are 1.61 * 10
-7Mol/cm
2
Embodiment 5
In the step (2), discharge power changes 30w into, and other conditions and step and embodiment 1 are identical.The mean thickness of gained film is that 661nm, anhydride group content are 5.59 * 10
-8Mol/cm
2
Embodiment 6
In the step (2), change 5min discharge time into, other conditions and step and embodiment 1 are identical.The mean thickness of gained film is that 110nm, anhydride group content are 1.29 * 10
-7Mol/cm
2
Embodiment 7
In the step (2), change 30 min discharge time into, other conditions and step and embodiment 1 are identical.The mean thickness 627nm of gained film, anhydride group content are 1.40 * 10
-7Mol/cm
2
Embodiment 8
In the step (2), discharge pressure changes 0-10Pa into, and other conditions and step and embodiment 1 are identical.Mean thickness 333 nm of gained film, anhydride group content are 1.76 * 10
-7Mol/cm
2
Embodiment 9
In the step (2), discharge pressure changes 40-50Pa into, and other conditions and step and embodiment 1 are identical.The average thick 282nm of gained film, anhydride group content are 1.53 * 10
-7Mol/cm
2
The basic explanation that above said content is only conceived for the present invention, and according to technical side of the present invention
Any equivalent transformation that case is done all should belong to protection scope of the present invention.
Claims (4)
1. the preparation method of a polymaleic anhydride film is characterized in that heating sublimation in plasma-deposited stove
The maleic anhydride monomer raw material, adopt lower temperature plasma technology, utilize glow discharge the plasma of gaseous state maleic anhydride monomer, make it produce living radical, between these living radicals or between free radical and the monomer polyaddition reaction occurs and form polymaleic anhydride film; The concrete steps of method are:
(1), take by weighing pulverous maleic anhydride monomer raw material with weighing bottle, this weighing bottle is fixed in the center of culture dish, again slide glass is fixed in this culture dish, make its be dispersed in weighing bottle around;
(2), step (1) gained system is placed plasma-deposited stove, take out base vacuum to 2.0 * 10
-3Behind the Pa, heat up 60～150 ℃, regulate chamber pressure 0～50Pa, under the power of 5～30w, discharge 5～30min can cross the uniform polymaleic anhydride film of last layer at slide glass.
2. the preparation method of a kind of polymaleic anhydride film as claimed in claim 1 is characterized in that described maleic anhydride monomer raw material is solid-state.
3. the preparation method of a kind of polymaleic anhydride film as claimed in claim 1, it is characterized in that preferred weighing bottle with 25mm * 25mm takes by weighing the pulverous maleic anhydride monomer raw material of 3.0g in the step (1), this weighing bottle is fixed in the center of 90mm culture dish, slide glass with 4 1mm * 25mm is fixed in this culture dish again, make its be dispersed in weighing bottle around.
4. the preparation method of 1 or 3 described polymaleic anhydride films as requested it is characterized in that the heating installation that carries in the plasma-deposited stove in the step (2) directly distils solid maleic anhydride monomer raw material, and the plasma aggregation deposition becomes film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010517374 CN101935821B (en) | 2010-10-25 | 2010-10-25 | Preparation method of polymaleic anhydride film |
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|---|---|---|---|
| CN 201010517374 CN101935821B (en) | 2010-10-25 | 2010-10-25 | Preparation method of polymaleic anhydride film |
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|---|---|
| CN101935821A CN101935821A (en) | 2011-01-05 |
| CN101935821B true CN101935821B (en) | 2013-03-06 |
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| CN 201010517374 Expired - Fee Related CN101935821B (en) | 2010-10-25 | 2010-10-25 | Preparation method of polymaleic anhydride film |
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| CN116925606A (en) * | 2022-03-29 | 2023-10-24 | 江苏菲沃泰纳米科技股份有限公司 | Hydrophilic coating, preparation method and device |
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2010
- 2010-10-25 CN CN 201010517374 patent/CN101935821B/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| 汤文杰，陈强，张跃飞，葛袁静.中频DBD等离子体聚合马来酸酐薄膜的研究.《真空科学与技术学报》.2007,第27卷(第3期),246-249. * |
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