CN106188587B - A kind of method that plasma initiation polymerisation in solution prepares temperature sensing polymer PNIPAM film - Google Patents

A kind of method that plasma initiation polymerisation in solution prepares temperature sensing polymer PNIPAM film Download PDF

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CN106188587B
CN106188587B CN201610574434.1A CN201610574434A CN106188587B CN 106188587 B CN106188587 B CN 106188587B CN 201610574434 A CN201610574434 A CN 201610574434A CN 106188587 B CN106188587 B CN 106188587B
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temperature sensing
film
sensing polymer
polymerisation
solution
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CN106188587A (en
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唐冬雁
杨旭
彭靖
吕海涛
齐小芳
包辛未
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Heilongjiang Industrial Technology Research Institute Asset Management Co ltd
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Harbin Institute of Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/52—Polymerisation initiated by wave energy or particle radiation by electric discharge, e.g. voltolisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/24—Homopolymers or copolymers of amides or imides

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Abstract

A kind of method that plasma initiation polymerisation in solution prepares temperature sensing polymer PNIPAM film, it is related to a kind of method for preparing temperature sensing polymer PNIPAM film.It will solve the problems, such as existing PNIPAM film synthetic method, and there are complex process, patterns to be easily destroyed, unstable chemcial property.Method: one, n-isopropyl acrylamide crystal is dissolved in ultrapure water, adds N, N- methylene-bisacrylamide；Two, the solution of step 1 configuration spreads over glass matrix surface, is placed in quartz reaction kettle, and sealing is passed through argon gas；Three, it is placed between plasma generator the two poles of the earth and is handled, obtain film, complete preparation after cleaning-drying.Using plasma of the present invention causes polymerisation in solution and forms a film, simple process, and step is few；Film forming is independent of matrix surface property；Pattern is not easy to be destroyed, and chemical property is stablized；Ingredient is single, biological nontoxic；Conducive to modification, structure can be modified, in many fields potential application prospect all with higher.

Description

A kind of plasma causes polymerisation in solution and prepares temperature sensing polymer PNIPAM film Method
Technical field
The present invention relates to a kind of methods for preparing temperature sensing polymer PNIPAM film.
Background technique
Stimuli responsive polymers are responded to environmental change, and the one of the variation of physical property or chemical property is generated Class macromolecule.Poly-N-isopropyl acrylamide (PNIPAM) is used as stimuli responsive polymers, has unique temperature-responsive row For.The lower critical solution temperature (LCST) of PNIPAM is 32 DEG C, and when temperature is lower than 32 DEG C, PNIPAM shows as hydrophily；Work as temperature Degree is higher than 32 DEG C, and PNIPAM shows as hydrophobicity.Due to this effective temperature-responsive of PNIPAM, in water process, drug control It releases, cell culture etc. is with a wide range of applications.
Currently, there are several types of self-assembled monolayers (SAMs), atom transfer for relatively conventional PNIPAM film synthetic method Free radical polymerization (ATRP), electron beam ionization, plasma graft, these types of method mainly include matrix preparation and add Work, matrix surface activation, initiator graft on surface, again by monomer matrix surface carry out be graft-polymerized four steps.Technique Complexity, step is various, wherein matrix surface activation degree and initiator grafting efficiency can all influence PNIPAM film forming degree and Cause monomer in the coverage rate of matrix surface and matrix is graft-polymerized；The PNIPAM film being grafted on matrix is unstable；Film Thickness is not easily controlled.In addition to this, the synthetic method of PNIPAM film is there are also sol-gel (sol-gel) method, but this method The film of preparation is easily soluble in solvent, and which greatly limits its applications in many fields.
Summary of the invention
The invention aims to solve existing PNIPAM film synthetic method, there are complex process, patterns to be easily destroyed, changes The unstable problem of property is learned, and a kind of plasma is provided and causes the side that polymerisation in solution prepares temperature sensing polymer PNIPAM film Method.
A kind of method that plasma initiation polymerisation in solution prepares temperature sensing polymer PNIPAM film, it is real according to the following steps It is existing:
One, 0.1-0.3g n-isopropyl acrylamide (NIPAM) crystal is taken, is dissolved in 4-6mL ultrapure water, it is added 0.004~ 0.04g N,N methylene bis acrylamide (MBA)；
Two, the solution that step 1 configures is taken into 0.2-0.3mL with syringe, equably spreads over glass matrix surface, so It is placed in quartz reaction kettle, seals, be passed through argon gas, 0~1L/min of flow velocity；
Three, the quartz reaction kettle of step 2 is placed between plasma generator the two poles of the earth, adjusts 0~45V of voltage, high pressure Discharge 0~5min, and macroscopic film can be obtained, then wash off unreacted monomer solution with ultrapure water, is dried in vacuo 5-7h completes the preparation of temperature sensing polymer PNIPAM film.
Beneficial effects of the present invention:
(1) using plasma causes, one-step polymerization film forming, and step is few；The temperature sensing polymer NIPAM film of preparation, tool There is surfacing, have the features such as fold and hydrophilic, aqueous stabilization and temperature sensitive type；
(2) simple process, without adding initiator, the also influence without the concern for solvent to polymerization；
(3) since polymerization occurs in solution surface, polymer and film do not have bonding action, so film forming is independent of matrix Surface nature；
(4) due to the addition of crosslinking agent, make monomer polymerization at macroscopic film, pattern is not easy to be destroyed, chemistry Property is stablized；
(5) because not using into initiator, organic solvent is not introduced, is not reacted with matrix surface, so making to polymerize Object thin film composition is single, biological nontoxic；
(6) by plasma-initiated polymerization, polymer film can be also modified, such as: being added and live in monomer solution Property monomer functionalization can be carried out to membrane structure by plasma-initiated polymerization, so that it is inhaled in many fields such as heavy metal ion The potential application value all with higher such as attached, cell culture, organizational project.
Detailed description of the invention
Fig. 1 is the schematic diagram figure that plasma of the present invention causes polymerisation in solution mechanism；
Fig. 2 is the infrared spectrum of preparation gained PNIPAM film in embodiment 1；Wherein 1 indicate NIPAM, 2 table PNIPAM；
Fig. 3 is the XPS analysis spectrogram of preparation gained PNIPAM film in embodiment 1, wherein 1 indicates C, 2 indicate N, and 3 indicate O；
Fig. 4 be embodiment 1 in preparation gained PNIPAM film XPS analysis spectrogram, wherein 1 indicate C-C, C-H bond type, 2 Indicate C-N bond type, 3 indicate that C=O bond type, a indicate total peak after fitting, and b indicates that C-C, C-H swarming after fitting, c indicate quasi- C-N swarming after conjunction, d indicate C=O swarming after fitting；
Fig. 5 is the histogram of hydrophobic angle of the preparation gained PNIPAM film at 32 DEG C and 38 DEG C in embodiment 1；
Fig. 6 is scanning electron microscope (SEM) figure of preparation gained PNIPAM film in embodiment 1.
Specific embodiment
Technical solution of the present invention is not limited to the specific embodiment of act set forth below, further include each specific embodiment it Between any combination.
Specific embodiment 1: a kind of plasma of present embodiment, which causes polymerisation in solution, prepares temperature sensing polymer The method of PNIPAM film is realized according to the following steps:
One, 0.1-0.3g n-isopropyl acrylamide crystal is taken, 4-6mL ultrapure water is dissolved in, 0.004~0.04g is added N,N methylene bis acrylamide；
Two, the solution that step 1 configures is taken into 0.2-0.3mL with syringe, equably spreads over glass matrix surface, so It is placed in quartz reaction kettle, seals, be passed through argon gas, 0~1L/min of flow velocity；
Three, the quartz reaction kettle of step 2 is placed between plasma generator the two poles of the earth, adjusts 0~45V of voltage, high pressure Discharge 0~5min, and macroscopic film can be obtained, then wash off unreacted monomer solution with ultrapure water, is dried in vacuo 5-7h completes the preparation of temperature sensing polymer PNIPAM film.
N,N methylene bis acrylamide is used as crosslinking agent in the present embodiment.
The present embodiment plasma initiated polymerization is commonly referred to be radical polymerization mechanism.As shown in Figure 1, polymerization Mechanism description is as follows: argon gas generates argon plasma under the conditions of electrion, and argon plasma has energy higher Activity is that C=C is activated in monomer NIPAM, generates C* free radical, polymerize between free radical.Due to crosslinking agent N, N- methylene The addition of base bisacrylamide (MBA), crosslinks, polymerization film formation.
During plasma causes synthesis PNIPAM film, monomer is added and not only affects the processing time, but also Affect the thickness and surface topography of film formation.With the increase of dosage of crosslinking agent, film formation time is shorter, film is thicker, film table Face is more smooth, the thicker surface folding the fewer.
Specific embodiment 2: present embodiment and specific embodiment one is not both to take 0.2g N- different in step 1 Propylacrylamide crystal is dissolved in 5mL ultrapure water, and 0.03g N, N- methylene-bisacrylamide is added.Other steps and parameter It is same as the specific embodiment one.
Specific embodiment 3: present embodiment and specific embodiment one or two not being both, by step in step 2 The solution of one configuration takes 0.25mL with syringe, equably spreads over glass matrix surface.Other steps and parameter and specific reality It is identical to apply mode one or two.
Specific embodiment 4: present embodiment and one of specific embodiment one to three is not both, lead in step 2 Enter argon gas, flow velocity 0.2L/min.Other steps and parameter are identical as one of specific embodiment one to three.
Specific embodiment 5: present embodiment and one of specific embodiment one to three is not both, lead in step 2 Enter argon gas, flow velocity 0.4L/min.Other steps and parameter are identical as one of specific embodiment one to three.
Specific embodiment 6: present embodiment and one of specific embodiment one to three is not both, lead in step 2 Enter argon gas, flow velocity 0.6L/min.Other steps and parameter are identical as one of specific embodiment one to three.
Specific embodiment 7: present embodiment and one of specific embodiment one to three is not both, lead in step 2 Enter argon gas, flow velocity 0.8L/min.Other steps and parameter are identical as one of specific embodiment one to three.
Specific embodiment 8: present embodiment and one of specific embodiment one to seven is not both to adjust in step 3 Save voltage 20V, electrion 3min.Other steps and parameter are identical as one of specific embodiment one to seven.
Specific embodiment 9: present embodiment and one of specific embodiment one to eight is not both to adjust in step 3 Save voltage 30V, electrion 4min.Other steps and parameter are identical as one of specific embodiment one to eight.
Specific embodiment 10: present embodiment and one of specific embodiment one to nine is not both, it is true in step 3 The dry 6h of sky.Other steps and parameter are identical as one of specific embodiment one to nine.
Beneficial effects of the present invention are verified by following embodiment:
Embodiment 1
A kind of method that plasma initiation polymerisation in solution prepares temperature sensing polymer PNIPAM film, it is real according to the following steps It is existing:
One, 0.2g n-isopropyl acrylamide crystal is taken, 5mL ultrapure water is dissolved in, 0.004g N, N- di-2-ethylhexylphosphine oxide is added Acrylamide；
Two, the solution that step 1 configures is taken into 0.25mL with syringe, equably spreads over glass matrix surface, then sets In in quartz reaction kettle, sealing is passed through argon gas, flow velocity 0.5L/min；
Three, the quartz reaction kettle of step 2 is placed between plasma generator the two poles of the earth, adjusts voltage 20V, height presses Macroscopic film can be obtained in electric 5min, then washes off unreacted monomer solution with ultrapure water, is dried in vacuo 6h, complete At the preparation of temperature sensing polymer PNIPAM film.
The temperature sensing polymer NIPAM film prepared in the present embodiment, 1 indicates monomer NIPAM infrared spectrum, and 2 indicate polymerization Object PNIPAM infrared spectrum analyzes (see Fig. 2) through infrared spectrum, and PNIPAM film component is single, remains the feature structure of monomer, Without other groups structure, there is biological non-toxicity.
Through XPS analysis (see Fig. 3 and Fig. 4), as a result referring to Tables 1 and 2, it is seen that the stable structure of polymer P NIPAM film.
Table 1
Element Peak number Peak position/eV Content/% Theoretical value
C 1 283.08 58.44 75.00
N 2 397.96 28.23 12.50
O 3 529.78 13.33 12.50
Table 2
Peak number Bond type Peak position/eV Peak area Ratio/% Theoretical value/%
1 C—C、C—H 285.0 5908.751 54.08 66.7
2 C—N 286.1 3060.595 28.00 16.7
3 C=O 287.8 1958.254 17.92 16.7
The temperature sensing polymer NIPAM film prepared in the present embodiment, have surfacing, have fold (see Fig. 6) and it is hydrophilic, The features such as water phase is stable and temperature sensitive type (see Fig. 5) is suitable for cell culture and cell absorption and heavy metal ion adsorbed equal studies.
Embodiment 2
A kind of method that plasma initiation polymerisation in solution prepares temperature sensing polymer PNIPAM film, it is real according to the following steps It is existing:
One, 0.2g n-isopropyl acrylamide crystal is taken, 5mL ultrapure water is dissolved in, 0.01g N, N- di-2-ethylhexylphosphine oxide third is added Acrylamide；
Two, the solution that step 1 configures is taken into 0.25mL with syringe, equably spreads over glass matrix surface, then sets In in quartz reaction kettle, sealing is passed through argon gas, flow velocity 0.6L/min；
Three, the quartz reaction kettle of step 2 is placed between plasma generator the two poles of the earth, adjusts voltage 25V, height presses Macroscopic film can be obtained in electric 5min, then washes off unreacted monomer solution with ultrapure water, is dried in vacuo 6h, complete At the preparation of temperature sensing polymer PNIPAM film.
The temperature sensing polymer NIPAM film prepared in the present embodiment, through detecting, chemical property is stablized, and film component is single, raw Object is nontoxic；Have the characteristics that surfacing, there is fold and hydrophilic, water phase is stable and temperature sensitive type.
Embodiment 3
A kind of method that plasma initiation polymerisation in solution prepares temperature sensing polymer PNIPAM film, it is real according to the following steps It is existing:
One, 0.2g n-isopropyl acrylamide crystal is taken, 5mL ultrapure water is dissolved in, 0.02g N, N- di-2-ethylhexylphosphine oxide third is added Acrylamide；
Two, the solution that step 1 configures is taken into 0.25mL with syringe, equably spreads over glass matrix surface, then sets In in quartz reaction kettle, sealing is passed through argon gas, flow velocity 0.4L/min；
Three, the quartz reaction kettle of step 2 is placed between plasma generator the two poles of the earth, adjusts voltage 15V, height presses Macroscopic film can be obtained in electric 5min, then washes off unreacted monomer solution with ultrapure water, is dried in vacuo 6h, complete At the preparation of temperature sensing polymer PNIPAM film.
The temperature sensing polymer NIPAM film prepared in the present embodiment, through detecting, chemical property is stablized, and film component is single, raw Object is nontoxic；Have the characteristics that surfacing, there is fold and hydrophilic, water phase is stable and temperature sensitive type.
Embodiment 4
A kind of method that plasma initiation polymerisation in solution prepares temperature sensing polymer PNIPAM film, it is real according to the following steps It is existing:
One, 0.2g n-isopropyl acrylamide crystal is taken, 5mL ultrapure water is dissolved in, 0.04g N, N- di-2-ethylhexylphosphine oxide third is added Acrylamide；
Two, the solution that step 1 configures is taken into 0.25mL with syringe, equably spreads over glass matrix surface, then sets In in quartz reaction kettle, sealing is passed through argon gas, flow velocity 0.8L/min；
Three, the quartz reaction kettle of step 2 is placed between plasma generator the two poles of the earth, adjusts voltage 30V, height presses Macroscopic film can be obtained in electric 5min, then washes off unreacted monomer solution with ultrapure water, is dried in vacuo 6h, complete At the preparation of temperature sensing polymer PNIPAM film.
The temperature sensing polymer NIPAM film prepared in the present embodiment, through detecting, chemical property is stablized, and film component is single, raw Object is nontoxic；Have the characteristics that surfacing, there is fold and hydrophilic, water phase is stable and temperature sensitive type.
Although describing the present invention herein with reference to specific embodiment, it should be understood that, these realities Apply the example that example is only principles and applications.It should therefore be understood that can be carried out to exemplary embodiment Many modifications, and can be designed that other arrangements, without departing from spirit of the invention as defined in the appended claims And range.It should be understood that different appurtenances can be combined by being different from mode described in original claim Benefit requires and feature described herein.It will also be appreciated that the feature in conjunction with described in separate embodiments can be used In other described embodiments.

Claims (8)

1. a kind of plasma causes the method that polymerisation in solution prepares temperature sensing polymer PNIPAM film, it is characterised in that it press with Lower step is realized:
One, 0.1-0.3g n-isopropyl acrylamide crystal is taken, 4-6mL ultrapure water is dissolved in, 0.004~0.04g N, N- is added Methylene-bisacrylamide；
Two, the solution that step 1 configures is taken into 0.2-0.3mL with syringe, equably spreads over glass matrix surface, then sets In in quartz reaction kettle, sealing is passed through argon gas, 0~1L/min of flow velocity；
Three, the quartz reaction kettle of step 2 is placed between plasma generator the two poles of the earth, adjusts voltage 15V~45V, height presses Macroscopic film can be obtained in electric 5min, then washes off unreacted monomer solution with ultrapure water, is dried in vacuo 5-7h, Complete the preparation of temperature sensing polymer PNIPAM film.
2. a kind of plasma causes the side that polymerisation in solution prepares temperature sensing polymer PNIPAM film according to claim 1 Method, it is characterised in that take 0.2g n-isopropyl acrylamide crystal in step 1, be dissolved in 5mL ultrapure water, 0.03gN, N- is added Methylene-bisacrylamide.
3. a kind of plasma causes the side that polymerisation in solution prepares temperature sensing polymer PNIPAM film according to claim 1 Method, it is characterised in that the solution that step 1 configures is taken into 0.25mL with syringe in step 2, equably spreads over glass matrix Surface.
4. a kind of plasma causes the side that polymerisation in solution prepares temperature sensing polymer PNIPAM film according to claim 1 Method, it is characterised in that argon gas, flow velocity 0.2L/min are passed through in step 2.
5. a kind of plasma causes the side that polymerisation in solution prepares temperature sensing polymer PNIPAM film according to claim 1 Method, it is characterised in that argon gas, flow velocity 0.4L/min are passed through in step 2.
6. a kind of plasma causes the side that polymerisation in solution prepares temperature sensing polymer PNIPAM film according to claim 1 Method, it is characterised in that argon gas, flow velocity 0.6L/min are passed through in step 2.
7. a kind of plasma causes the side that polymerisation in solution prepares temperature sensing polymer PNIPAM film according to claim 1 Method, it is characterised in that argon gas, flow velocity 0.8L/min are passed through in step 2.
8. a kind of plasma causes the side that polymerisation in solution prepares temperature sensing polymer PNIPAM film according to claim 1 Method, it is characterised in that 6h is dried in vacuo in step 3.
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CN101023123A (en) * 2004-08-31 2007-08-22 株式会社奥西珍尼克斯 Thin-filmy polymeric structure and method of preparing the same
CN101045797A (en) * 2007-03-30 2007-10-03 东华大学 Preparation of moisture controllable polymer composite film and its application
CN102250373A (en) * 2011-05-27 2011-11-23 天津工业大学 Micron-nano topological smart membrane and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101023123A (en) * 2004-08-31 2007-08-22 株式会社奥西珍尼克斯 Thin-filmy polymeric structure and method of preparing the same
CN101045797A (en) * 2007-03-30 2007-10-03 东华大学 Preparation of moisture controllable polymer composite film and its application
CN102250373A (en) * 2011-05-27 2011-11-23 天津工业大学 Micron-nano topological smart membrane and preparation method thereof

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