CN1064379C - Porous figure film of alternate styrene-maleic anhydride copolymer and its preparation - Google Patents
Porous figure film of alternate styrene-maleic anhydride copolymer and its preparation Download PDFInfo
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- CN1064379C CN1064379C CN98111598A CN98111598A CN1064379C CN 1064379 C CN1064379 C CN 1064379C CN 98111598 A CN98111598 A CN 98111598A CN 98111598 A CN98111598 A CN 98111598A CN 1064379 C CN1064379 C CN 1064379C
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- maleic anhydride
- sma
- anhydride copolymer
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- 229920000147 Styrene maleic anhydride Polymers 0.000 title claims abstract description 41
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000011148 porous material Substances 0.000 claims abstract description 10
- 239000013078 crystal Substances 0.000 claims abstract description 7
- 239000002131 composite material Substances 0.000 claims abstract description 3
- 239000002184 metal Substances 0.000 claims abstract description 3
- 239000004065 semiconductor Substances 0.000 claims abstract description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 30
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 21
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 238000009826 distribution Methods 0.000 claims description 10
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 6
- 239000010453 quartz Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 230000003750 conditioning effect Effects 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- 239000002105 nanoparticle Substances 0.000 claims description 3
- 238000005498 polishing Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000000413 hydrolysate Substances 0.000 claims description 2
- 239000010408 film Substances 0.000 claims 9
- 238000004519 manufacturing process Methods 0.000 claims 4
- 239000010409 thin film Substances 0.000 claims 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 229920001577 copolymer Polymers 0.000 abstract description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 abstract description 2
- 238000004377 microelectronic Methods 0.000 abstract description 2
- 230000005622 photoelectricity Effects 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 238000009827 uniform distribution Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 7
- 229920002521 macromolecule Polymers 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000012043 crude product Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- CSCPPACGZOOCGX-WFGJKAKNSA-N deuterated acetone Substances [2H]C([2H])([2H])C(=O)C([2H])([2H])[2H] CSCPPACGZOOCGX-WFGJKAKNSA-N 0.000 description 1
- 238000000609 electron-beam lithography Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000009415 formwork Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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- Application Of Or Painting With Fluid Materials (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The present invention relates to the synthesis of an alternate styrene-maleic anhydride copolymer, and a preparation method of a porous figure film of the alternate styrene-maleic anhydride copolymer. In the present invention, the alternate styrene-maleic anhydride copolymer with low molecular weight and monodispersity is synthesized by a solution polymerization method; the acidity of a solution of the copolymer is regulated into stronger acidity, and submicron porous figure films with uniform distribution and uniform pore sizes are obtained on an inorganic substrate by a rotating film forming method. The films can be used as organic templates, and metal, semiconductors, etc. can be assembled in pores in the films to obtain a composite system, an orientated monocrystal or binary crystal, etc.; the films have significant application value in the fields of microelectronics, photoelectricity, sensing devices, etc.
Description
The present invention relates to porous figure film of alternate styrene-maleic anhydride copolymer and preparation method thereof.
In recent years, ((thickness is subjected to pay attention in the research of 100～1000nm) weave surface pattern [referring to J.Polym.Sci.Part B:Polym.Phys.34,3017～3024 (1996) macromolecule hyper-film deeply for thickness＜100nm) or film; Macromolecules 29,5010～5016 (1996); J.Polym.Sci.Part B:Polym.Phys.36,191～200 (1998); Macromolecules 31,857～862 (1998); Macromolecules 31,863～869 (1998); J.Appl.Polym.Sci.68,503～508 (1998)], because of as functional film material, the pattern on polymeric membrane surface plays an important role to the decision behaviour.Yet research mainly is limited to the polymer blended system of binary, and focuses on the molecular motion of air-macromolecule interfacial and the orientation of chain.In the co-mixing system, because of the difference of component surface free energy, under the modulation of temperature and composition, the co-mixing system film surface can produce " hole " style structure [referring to: Macromolecules 29,5010～5016 (1996); J.Polym.Sci.Part B:Polym.Phys.36,191～200 (1998)], but in these co-mixing systems, the distribution of hole and geometrical dimension be heterogeneity very.
By inducing of submicron hole organic formwork, in the template hole, form oriented single crystal or binary crystal, this development field at submicron order electron device and photonic bandgap material has important use to be worth.The formation of these templates normally by technology such as electron beam lithography or photoetching realize [referring to: Nature 385,321～324 (1997); Sciene 272,85～87 (1996)], this requires very high to technology and equipment.
Under study for action, we utilize special construction and chemical, the physical properties of alternate styrene-maleic anhydride copolymer (SMA), design and obtain geometrical dimension and the distribution porous figure film than homogeneous.According to the retrieval, this porous figure film that is formed by single high molecular component does not still have report.
The object of the invention provides porous figure film and preparation method by the alternate styrene-maleic anhydride copolymer preparation.
The foregoing invention purpose is achieved in that vinylbenzene, maleic anhydride is dissolved in the benzene solvent, is initiator with the benzoyl peroxide, obtains alternate styrene-maleic anhydride copolymer; It is dissolved in the tetrahydrofuran (THF), makes solution, in this solution, add entry, again with hydrochloric acid conditioning solution to acid, go up the rotation film forming in the lining base after the hydrolysis, promptly obtain mean pore size at submicron order and distribute than the porous figure film of homogeneous.
The present invention is described in detail below in detail: vinylbenzene (S), maleic anhydride (M) are dissolved in the benzene solvent with 1: 1 mol ratio, with benzoyl peroxide (BPO) is initiator, obtains lower molecular weight and the very narrow alternate styrene-maleic anhydride copolymer (SMA) of molecular weight distribution by solution polymerization; SMA is dissolved in the tetrahydrofuran (THF), makes the solution that concentration is 10mg/ml; In this solution, add entry, SMA and H
2The weight ratio of O is 3: 1-2, again with hydrochloric acid conditioning solution to acid pH=1-1.5; Hydrolysis is after 2 hours under the room temperature, and the rotating speed of going up with 1300-1500rpm in the lining base rotates film forming, promptly obtains mean pore size at 0.5-0.7 μ m, and distributes than the submicron order porous figure film of homogeneous.
The used lining base of the present invention can be monocrystalline silicon piece, polishing quartz plate or slide glass.
The inventive method also can utilize the hydrolysate of SMA to replace SMA to obtain porous figure film.
The inventive method, the concentration of also available change SMA solution obtains the porous figure film of the different apertures and the degree of depth.
Characteristics of the present invention are that the preparation of porous figure film is simple, only need carry out at normal temperatures and pressures; The film porous figure area of preparing is big, and aperture and distribution are than homogeneous; It is compound to can be used as submicron such as template and metal, semi-conductor or nano particle, the preparation composite film material, and prepare oriented single crystal and binary crystal etc. as the confinement template.In addition, the formation of Central Asia of the present invention micron order hole film confinement growth that can be submicron or nano particle provides template.These have important use to be worth in fields such as the adjustable microelectronics of performance, photoelectricity, susceptible device susceptores.
Synthesizing of embodiment 1. (1) alternate styrene-maleic anhydride copolymers (SMA):
The heavily steaming benzene that in 500 milliliter of three neck round bottom burns, adds vinylbenzene that 18 milliliters of purifying cross, 15 gram maleic anhydrides and 400 milliliters, in 60 ℃ be stirred to the solution clarification after, add the benzoyl peroxide that a small amount of recrystallization is crossed; The temperature of solution is raised to 80～81 ℃, solution muddiness after tens minutes, allow reactant under vigorous stirring in this thermotonus 1 hour; Then, stop heating, allow reactant naturally cool to room temperature; The suction filtration product, and with an amount of benzene washing three times, drain and obtain the SMA crude product.Be scattered in the SMA crude product in the capacity benzene and refluxed 24 hours, suction filtration, again with an amount of benzene washing, product is in 80 ℃ of vacuum-dryings 48 hours, heavily about 27 grams of final product.
With acetone is solvent, and the polystyrene of monodispersity is a standard specimen, carries out the molecular weight determination of product on WATERS 150-C gel permeation chromatography (GPC), data show synthesize the number-average molecular weight (M of SMA
n) be 2560, M
w/ M
n=1.04 (wherein, M
wBe weight-average molecular weight).The proton nmr spectra data show that the molar fraction of styrene units on the copolymer molecule chain is 0.51, and carbon-13 nmr spectra has shown the copolymer molecule chain structure of alternating growth.The nuclear magnetic resonance spectrum of product is seen accompanying drawing 1, and the infrared spectra of product is seen curve A in the accompanying drawing 2.(2) the upward preparation of porous figure film of monocrystalline silicon piece lining base:
0.30g SMA was stirred 15 hours in the 30ml tetrahydrofuran (THF), and obtaining concentration is the SMA tetrahydrofuran solution of 1%g/ml.Add the 0.16ml deionized water, stirred 10 minutes, with the acidity of an amount of concentrated hydrochloric acid regulator solution to pH=1～1.5; Allow solution stir under room temperature 2 hours, be hydrolyzed, this step reaction is characterized by curve B in the accompanying drawing 2; Drip two solution on clean monocrystalline silicon piece lining base with dropper, and with rotating speed film forming on film former of 1400rpm.Recording the film mean thickness that this process obtains with ellipsometer is 232nm.Atomic force microscope (AFM) records the mean diameter d=0.60 μ m of hole in the film, standard deviation S d=0.13 μ m; Mean depth h=206.12nm, standard deviation S
d=6.73nm.The atomic power of film surface appearance is micro-resemble and imaging area 10 * 10 μ m in pore size distribution see accompanying drawing 3 and 4; The stereoscan photograph of film surface is seen accompanying drawing 5.
Synthesizing of embodiment 2. (1) alternate styrene-maleic anhydride copolymers (SMA): with embodiment 1.(2) the upward preparation of porous figure film of slide glass and quartz plate lining base:
0.30gSMA was stirred 15 hours in the 30ml tetrahydrofuran (THF), and obtaining concentration is the SMA tetrahydrofuran solution of 1%g/ml.Add the 0.10ml deionized water, stirred 10 minutes, to pH=1～1.5, allow solution under room temperature, stir 2 hours, be hydrolyzed with the acidity of an amount of concentrated hydrochloric acid regulator solution; Drip two solution on clean glass slide and polishing quartz plate lining base with dropper, and with rotating speed film forming on film former of 1400rpm.The film mean thickness can embodiment 1 in film on the monocrystalline silicon piece be reference.The mean diameter that AFM records hole in the slide glass upper film is d=0.53 μ m, its standard deviation S
d=0.11 μ m; Mean depth h=204.75nm, its standard deviation S
d=9.43nm.The mean diameter that AFM records hole in the quartz plate upper film is d=0.53 μ m, its standard deviation S
d=0.13 μ m, mean depth h=201.13nm, its standard deviation S
d=8.69nm, the three-dimensional atomic power of film surface appearance is micro-resemble and imaging area 10 * 10 μ m in pore size distribution see accompanying drawing 6 and 7.
Description of drawings:
Fig. 1. proton nmr spectra of product (A) and carbon spectrum (B); It wherein is solvent with the deuterated acetone.
Fig. 2. by making the film sample in the tetrahydrofuran solution, record product S MA and form before the film (curve A) and the back infrared spectra of (curve B).
Fig. 3. monocrystalline silicon piece lining base is gone up the three-dimensional (A) and micro-elephant of two dimension (B) atomic power of SMA porous figure film.
Fig. 4. monocrystalline silicon piece lining base is gone up the pore size distribution (10 * 10 μ m) in the SMA porous figure film.
Fig. 5. the stereoscan photograph of Fig. 3 film.
Fig. 6. pore size distribution (B) (10 * 10 μ m) in micro-elephant of three-dimensional atomic power (A) of the basic upward SMA porous figure film of slide glass lining and the film.
Fig. 7. pore size distribution (B) (10 * 10 μ m) in micro-elephant of three-dimensional atomic power (A) of the basic upward SMA porous figure film of quartz plate lining and the film.
Claims (7)
1. the preparation method of a porous figure film of alternate styrene-maleic anhydride copolymer, it is characterized in that, (SMA) is dissolved in the tetrahydrofuran (THF) with low-molecular-weight alternate styrene-maleic anhydride copolymer, in this solution, add entry, extremely acid with hydrochloric acid conditioning solution again, stir under the room temperature, go up the rotation film forming in lining base, promptly distributed and the aperture than the porous figure film of homogeneous.
2. method for manufacturing thin film as claimed in claim 1 is characterized in that, described vinylbenzene, maleic anhydride are dissolved in the benzene solvent with 1: 1 mol ratio, are initiator with the benzoyl peroxide; SMA is dissolved in the tetrahydrofuran (THF), makes the solution that concentration is 10mg/ml; Add water again, make SMA and H
2The weight ratio of O is 3: 1-2, and again with hydrochloric acid conditioning solution pH=1-1.5, hydrolysis is 2 hours under the room temperature, and the rotating speed with 1300-1500rpm on the lining base rotates film forming.
3. method for manufacturing thin film as claimed in claim 1 is characterized in that, described lining base can be monocrystalline silicon piece, polishing quartz plate or slide glass.
4. method for manufacturing thin film as claimed in claim 1 is characterized in that, also can utilize the hydrolysate of SMA to replace SMA to obtain porous figure film.
5. method for manufacturing thin film as claimed in claim 1 is characterized in that, as long as change the porous figure film that the concentration of SMA solution just can obtain the different apertures and the degree of depth.
6. with the porous figure film of alternate styrene-maleic anhydride copolymer of claim 1 method preparation, it is characterized in that the porous figure area is big, aperture and distribution are than homogeneous, and mean pore size is at 0.5--0.7 μ m.
7. porous figure film of alternate styrene-maleic anhydride copolymer as claimed in claim 6, it is characterized in that, can it is compound as template and metal or semi-conductor submicron or nano particle, the preparation composite film material, and prepare oriented single crystal and binary crystal as the confinement template.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98111598A CN1064379C (en) | 1998-12-05 | 1998-12-05 | Porous figure film of alternate styrene-maleic anhydride copolymer and its preparation |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98111598A CN1064379C (en) | 1998-12-05 | 1998-12-05 | Porous figure film of alternate styrene-maleic anhydride copolymer and its preparation |
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| Publication Number | Publication Date |
|---|---|
| CN1224731A CN1224731A (en) | 1999-08-04 |
| CN1064379C true CN1064379C (en) | 2001-04-11 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98111598A Expired - Fee Related CN1064379C (en) | 1998-12-05 | 1998-12-05 | Porous figure film of alternate styrene-maleic anhydride copolymer and its preparation |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0114851A1 (en) * | 1982-03-05 | 1984-08-08 | National Research Development Corporation | Polymeric films |
| GB2198741A (en) * | 1984-04-03 | 1988-06-22 | Wolfen Filmfab Veb | Photopolymerisable materials |
| US5641608A (en) * | 1995-10-23 | 1997-06-24 | Macdermid, Incorporated | Direct imaging process for forming resist pattern on a surface and use thereof in fabricating printing plates |
-
1998
- 1998-12-05 CN CN98111598A patent/CN1064379C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0114851A1 (en) * | 1982-03-05 | 1984-08-08 | National Research Development Corporation | Polymeric films |
| GB2198741A (en) * | 1984-04-03 | 1988-06-22 | Wolfen Filmfab Veb | Photopolymerisable materials |
| US5641608A (en) * | 1995-10-23 | 1997-06-24 | Macdermid, Incorporated | Direct imaging process for forming resist pattern on a surface and use thereof in fabricating printing plates |
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| Publication number | Publication date |
|---|---|
| CN1224731A (en) | 1999-08-04 |
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