CN101045796A - Ferrocene base full conjugate polyaromatic superhydraulic film and preparation method - Google Patents
Ferrocene base full conjugate polyaromatic superhydraulic film and preparation method Download PDFInfo
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- CN101045796A CN101045796A CN 200710098501 CN200710098501A CN101045796A CN 101045796 A CN101045796 A CN 101045796A CN 200710098501 CN200710098501 CN 200710098501 CN 200710098501 A CN200710098501 A CN 200710098501A CN 101045796 A CN101045796 A CN 101045796A
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Abstract
This invention belongs to function stuff, surface chemistry region, relate to a kind of ferrocenyl full conjugate poly- aromatic hydrocarbon, super hydrophobic film and its preparation method. This hydrophobic film is formed by free depositting of conjugate poly- aromatic hydrocarbon which possess super branching structure. The super branching structure conjugated polymer is generated by that conjugate double alkyne monomer and conjugate ferrocenyl mono alkyne monomer takes alkyne- alkyne loop trimerization under catalyzer action. This kind of polymer possess favorable solubility, be able to through sedimentary way to carry out embellish to body surface, bring body surface super hydrophobic property; and by test the static surface contact angle of it and water is greater than 150 deg.
Description
Technical field
The invention belongs to functional materials, surface chemistry field, relate to class ferrocene base full conjugate polyaromatic superhydraulic film and preparation method thereof.
Background technology
Wetting property is a key character of solid surface, and hydrophobic performance conduct a kind of manifestation mode wherein, extremely wide application value is all arranged in industrial and agricultural production and daily life, for example, it can be used for waterproof, snow defence, anti-icing, anti-pollution, anti-oxidant and prevent conduction of current etc.River thunder group is at " Advanced Materials " magazine 2002,14 (24), the article of delivering on 1857～1860 " super hydrophobic surface: from nature to bionical " (Lin Feng, Lei Jiang, et al.super-hydrophobic surfaces:From Natural to Artificial.Adv.Mater.), the super-hydrophobicity that discloses natural lotus leaf surface is by its surface microstructure and chemical constitution decision, and wherein the surface micron plays important effect with nanophase bonded rough surface structure to super-hydrophobicity.
Usually, the method that improves solid hydrophobic surface mainly contains two kinds: the one, modify solid surface with material such as fluorochemicals with low surface energy; The 2nd, the degree of roughness of increase solid surface.At present, this Chinese invention patent publication number CN 1544482A discloses a kind of usefulness
60Co irradiation prepares the method for super-hydrophobic polymeric film, with Fluorine containing olefine as hydrophobic monomer, in non-Fluorine containing olefine atmosphere,
60Radiation polymerization in the Co irradiation field, normal temperature and pressure prepare super-hydrophobic polymeric film, and itself and water static contact angle are greater than 130 °." science " magazine 2003,299, article " simple a kind of plastics are converted into based superhydrophobic thin films " (H.Yildirim Erbil, A.Levent Demirel, the Yonca Avci of report on 1377～1380, Olcay Mert, Transformation of a Simple Plastic into a Superhydrophobic Surface Science.), is dissolved in isotatic polypropylene in the p-Xylol, with non-solvent precipitated crystal at a certain temperature, obtain super-hydrophobic film then.We find when the hyperbranched conjugated polyaromatic of research, polymers soln is added drop-wise in the non-solvent, solvent is slowly volatilized, finally formed a kind of like the fractal micro nano structure (seeing accompanying drawing 4) of plant leaf vein at solid surface, this surface has good hydrophobic character, its to the static contact angle of water greater than 150 °.
Summary of the invention
One of purpose of the present invention has been to synthesize a kind of brand-new hyperbranched polymer, utilizes the unique texture of polymkeric substance to form and a kind ofly makes body surface have superhydrophobic property like the fractal micro nano structure of plant leaf vein.
Two of purpose of the present invention provides the method that a kind of preparation has the hydrophobic polymer film of micro nano structure.Utilize the different solubility of polymkeric substance in good solvent and poor solvent, the object that will handle is placed in the poor solvent of polymkeric substance, and the drips of solution of polymkeric substance is added in the poor solvent, treats that solvent slowly volatilizees, polymkeric substance will slowly be deposited on object surfaces, makes object have superhydrophobic property.
The present invention is made up of ferrocenyl full conjugate hyperbranched poly aromatic hydrocarbons; By modifying in the solid surface deposition after the polymer dissolution, make solid surface have superhydrophobic property.
Ferrocenyl hyperbranched polyaromatic is to obtain by the reaction of alkynes-alkynes ring trimeric method, and temperature of reaction is room temperature～100 ℃.
The employed monomer of polymerization is two alkynes of conjugation and the single alkynes of conjugation, and single alkynes monomer contains ferrocene group, and the polyaromatic of formation is a dissaving structure, and concrete structure is as follows:
The employed catalyzer of polyreaction is Co system, Ni system, Ta system, and catalyst concn is 5mM～30mM.Wherein concrete catalyzer is as follows:
Co is Cp
2Co, CpCo (CH
2=CH
2)
2, CpCo (CO)
2, Co
2(CO)
8
Ni is Cp
2Ni, Ni (CH
2=CH
2)
2, (Ph
3P) Ni (CO)
3, (Ph
3P)
2Ni (CO)
2,
[(NCCH
2CH
2)
3P]Ni(CO)
2；
Ta is TaCl
5, TaBr
5, TaI
5, TaCl
5-Ph
4Sn, TaBr
5-Ph
4Sn, TaI
5-Ph
4Sn.
The film that hyperbranched poly aromatic hydrocarbons forms is body surface to be modified in the sedimentary method of solid surface by polymers soln, makes body surface have superhydrophobic property, to the static contact angle of water at 130～160 °.
The step of preparation super hydrophobic surface is:
A), use solvent to be tetrahydrofuran (THF), dioxane, chloroform, methylene dichloride, toluene with polymer dissolution;
B) polymers soln is added drop-wise to make polymer precipitation, poor solvent in the poor solvent be normal hexane, methyl alcohol, hexanaphthene, sherwood oil, acetone;
C) object that is used to carry super-hydrophobic polymeric film comprises silicon chip, quartz plate, sheet glass, tinsel, polymeric film.
The present invention prepares the method for super hydrophobic surface, be the solution of in good solvent, preparing polymkeric substance by polymer dissolution, drip then in the poor solvent of polymkeric substance and be deposited in solid surface, by a kind of micro nano structure of the spontaneous formation of the molecular interaction in the deposition process, thereby make adorned body surface have superhydrophobic property.The solvent that is used for dissolve polymer during the preparation based superhydrophobic thin films is tetrahydrofuran (THF), dioxane, chloroform, methylene dichloride, toluene; The poor solvent of precipitation polymers is a normal hexane, methyl alcohol, hexanaphthene, sherwood oil, acetone.Concrete preparation process is as follows:
(1) with polymer dissolution in good solvent, obtain polymers soln;
(2) object that will handle is put into the bottom of poor solvent, and treat surface is added drop-wise to polymers soln then and makes polymer precipitation in the poor solvent up;
(3) utilize solvent to volatilize naturally, polymkeric substance forms micro-nano aggregated structure when slowly depositing; Treat that solvent evaporates finishes, body surface promptly forms the based superhydrophobic thin films upper layer, and its static contact angle can reach 150 °～160 °.
The method that the present invention makes based superhydrophobic thin films is simple, easy handling, and be suitable for the large-area preparation super hydrophobic surface.Another characteristics of the present invention are the interaction between the π-pi-conjugated group that utilizes in the dissaving structure and the solid space steric hindrance of ferrocene group itself, make and form the fractal structure of a kind of similar plants vein in the polymer deposition process, this structure makes processed surface have excellent hydrophobic property, do not need fluoridation, thereby avoided the harm of fluorine cpd human body.
Description of drawings
The polymkeric substance that obtains among Fig. 1-embodiment 7 static contact angle photo that surface treatment obtains to silicon substrate
The polymkeric substance that obtains among Fig. 2-embodiment 8 static contact angle photo that surface treatment obtains to silicon substrate
The electron scanning micrograph that the polymkeric substance that obtains among Fig. 3-embodiment 8 obtains after to the silicon substrate surface treatment
Embodiment
The present invention will be further described below in conjunction with drawings and Examples.
One. the preparation of hyperbranched poly aromatic hydrocarbons
Embodiment 1
(1) biphenyl diine 1a 0.2022g (1mmol) and ferrocene list alkynes 2a 0.3122g (1mmol) are joined in the Schlenk test tube of prebake conditions, anti-beyond the Great Wall then chewing-gum plug makes system airtight.And to its vacuumize, inflated with nitrogen, circulation repeatedly three times.
(2) the toluene 20.0mL that drying is crossed injected 0.0540g afterwards and encircles penta dicarbapentaborane cobalt catalyst by in the syringe injecting tube, 65 ℃ of reactions 2 hours.
(3) reaction finishes, and reaction solution is deposited in the 500mL methyl alcohol by the cotton fibre strainer.Collecting precipitation dissolves the back secondary sedimentation again with chloroform.At last the solid of collecting is dried to constant weight under vacuum, gets red powder 0.1955g, productive rate 38.0%.
Embodiment 2
(1) biphenyl diine 1a 0.2022g (1mmol) and ferrocene list alkynes 2a 0.3122g (1mmol) are joined in the Schlenk test tube of prebake conditions, anti-beyond the Great Wall then chewing-gum plug makes system airtight.And to its vacuumize, inflated with nitrogen, circulation repeatedly three times.
(2) the toluene 20.0mL that drying is crossed injected 0.0540g afterwards and encircles penta dicarbapentaborane cobalt catalyst by in the syringe injecting tube, 65 ℃ of reactions 6 hours.
(3) reaction finishes, and reaction solution is deposited in the 500mL methyl alcohol by the cotton fibre strainer.Collecting precipitation dissolves the back secondary sedimentation again with chloroform.At last the solid of collecting is dried to constant weight under vacuum, gets red powder 0.3602g, productive rate 70.0%.
Embodiment 3
(1) biphenyl diine 1a 0.1011g (0.5mmol) and ferrocene list alkynes 2b 0.1591g (0.5mmol) are joined in the Schlenk test tube of prebake conditions, anti-beyond the Great Wall then chewing-gum plug makes system airtight.And to its vacuumize, inflated with nitrogen, circulation repeatedly three times.
(2) the toluene 20.0mL that drying is crossed injected 0.0540g afterwards and encircles penta dicarbapentaborane cobalt catalyst by in the syringe injecting tube, 65 ℃ of reactions 6 hours.
(3) reaction finishes, and reaction solution is deposited in the 500mL methyl alcohol by the cotton fibre strainer.Collecting precipitation dissolves the back secondary sedimentation again with chloroform.At last the solid of collecting is dried to constant weight under vacuum, gets red powder 0.1525g, productive rate 58.6%.
Embodiment 4
(1) in glove box ferrocene diine 1c 0.1096g (0.25mmol) and ferrocene list alkynes 2a 0.0780g (0.25mmol) are joined among the Schlenk test tube A of prebake conditions, anti-beyond the Great Wall then chewing-gum plug makes system airtight.In another Schlenk test tube B, add TaCl
50.0403g (0.1125mmol) and Ph
4Sn 0.0480g (0.1125mmol), also anti-beyond the Great Wall chewing-gum plug makes system airtight.
(2) the toluene 10.0mL that drying is crossed passes through among the syringe injecting tube A, 5.0mL injecting tube B.At room temperature stirred separately 15 minutes.
(3) solution among the test tube B is taken out among the injecting tube A by syringe, reaction is 30 minutes under the room temperature.
(4) reaction finishes, and reaction solution is deposited in the 500mL methyl alcohol by the cotton fibre strainer.Collecting precipitation dissolves the back secondary sedimentation again with chloroform.At last the solid of collecting is dried to constant weight under vacuum, gets sorrel powder 0.1768g, productive rate 94.2%.
Embodiment 5
(1) in glove box ferrocene diine 1c 0.1096g (0.25mmol) and ferrocene list alkynes 2a 0.0780g (0.25mmol) are joined among the Schlenk test tube A of prebake conditions, anti-beyond the Great Wall then chewing-gum plug makes system airtight.In another Schlenk test tube B, add TaBr
50.0653g (0.1125mmol) and Ph
4Sn 0.0480g (0.1125mmol), also anti-beyond the Great Wall chewing-gum plug makes system airtight.
(2) the toluene 10.0mL that drying is crossed passes through among the syringe injecting tube A, 5.0mL injecting tube B.At room temperature stirred separately 15 minutes.
(3) solution among the test tube B is taken out among the injecting tube A by syringe, reaction is 30 minutes under the room temperature.
(4) reaction finishes, and reaction solution is deposited in the 500mL methyl alcohol by the cotton fibre strainer.Collecting precipitation dissolves the back secondary sedimentation again with chloroform.At last the solid of collecting is dried to constant weight under vacuum, gets sorrel powder 0.1189g, productive rate 63.4%.
Embodiment 6
(1) in glove box ferrocene diine 1c 0.0438g (0.1mmol) and ferrocene list alkynes 2a 0.0156g (0.05mmol) are joined among the Schlenk test tube A of prebake conditions, anti-beyond the Great Wall then chewing-gum plug makes system airtight.In another Schlenk test tube B, add TaBr
50.0218g (0.0375mmol), also anti-beyond the Great Wall chewing-gum plug makes system airtight.
(2) the toluene 10.0mL that drying is crossed passes through among the syringe injecting tube A, 5.0mL injecting tube B.At room temperature stirred separately 15 minutes.
(3) solution among the test tube B is taken out among the injecting tube A by syringe, reaction is 30 minutes under the room temperature.
(4) reaction finishes, and reaction solution is deposited in the 500mL methyl alcohol by the cotton fibre strainer.Collecting precipitation dissolves the back secondary sedimentation again with chloroform.At last the solid of collecting is dried to constant weight under vacuum, gets sorrel powder 0.0517g, productive rate 87.1%.
Two. the preparation of super hydrophobic surface
Embodiment 7
(1) polymkeric substance that obtains among the embodiment 2 is made the tetrahydrofuran solution of 0.5mg/mL.Silicon substrate is placed in the beaker that fills 10mL methyl alcohol, splashes into the polymkeric substance tetrahydrofuran solution of 1mL 0.5mg/mL then.Make its slow precipitation.Treat that solvent evaporates falls the back and obtain the homogeneous polymer film on the silicon substrate.
(2) will be with vacuum-drying under the silicon substrate room temperature of polymeric film 24 hours.Measure static contact angle then.As accompanying drawing 1, its contact angle to water is 155 °.
Embodiment 8
(1) polymkeric substance that obtains among the embodiment 4 is made the tetrahydrofuran solution of 0.5mg/mL.Silicon substrate is placed in the beaker that fills the 10mL normal hexane, splashes into the polymkeric substance tetrahydrofuran solution of 1mL 0.5mg/mL then.Make its slow precipitation.Treat to obtain the homogeneous polymer film on the intact silicon substrate of solvent evaporates.
(2) will be with vacuum-drying under the silicon substrate room temperature of polymeric film 24 hours.Measure static contact angle then.As accompanying drawing 2, its contact angle to water is 147 °.And this is handled the surface observe with scanning electronic microscope, a kind of micro nano structure of similar plants vein shape of having found polymer formation is as accompanying drawing 3.
Claims (6)
1 one kinds of ferrocene base full conjugate polyaromatic superhydraulic films and preparation method, it is characterized in that: it is made up of ferrocenyl full conjugate hyperbranched poly aromatic hydrocarbons; By modifying in the solid surface deposition after the polymer dissolution, make solid surface have superhydrophobic property.
2 a kind of ferrocene base full conjugate polyaromatic superhydraulic film as claimed in claim 1 and preparation methods is characterized in that: ferrocenyl hyperbranched polyaromatic is to obtain by the reaction of alkynes-alkynes ring trimeric method, and temperature of reaction is room temperature～100 ℃.
3 a kind of ferrocene base full conjugate polyaromatic superhydraulic film as claimed in claim 1 and preparation methods, it is characterized in that: the employed monomer of polymerization is two alkynes of conjugation and the single alkynes of conjugation, and single alkynes monomer contains ferrocene group, and the polyaromatic of formation is a dissaving structure, and concrete structure is as follows:
4 a kind of ferrocene base full conjugate polyaromatic superhydraulic film as claimed in claim 1 and preparation methods is characterized in that: the employed catalyzer of polyreaction is Co system, Ni system, Ta system, and catalyst concn is 5mM～30mM.Wherein concrete catalyzer is as follows:
Co is Cp
2Co, CpCo (CH
2=CH
2)
2, CpCo (CO)
2, Co
2(CO)
8
Ni is Cp
2Ni, Ni (CH
2=CH
2)
2, (Ph
3P) Ni (CO)
3, (Ph
3P)
2Ni (CO)
2, [(NCCH
2CH
2)
3P] Ni (CO)
2
Ta is TaCl
5, TaBr
5, TaI
5, TaCl
5-Ph
4Sn, TaBr
5-Ph
4Sn, TaI
5-Ph
4Sn.
5 a kind of ferrocene base full conjugate polyaromatic superhydraulic film as claimed in claim 1 and preparation methods, it is characterized in that: the film that hyperbranched poly aromatic hydrocarbons forms is body surface to be modified in the sedimentary method of solid surface by polymers soln, make body surface have superhydrophobic property, to the static contact angle of water at 130～160 °.
The preparation method of 6 a kind of ferrocene base full conjugate polyaromatic superhydraulic films as claimed in claim 5 is characterized in that: the step of preparation super hydrophobic surface is as follows:
A), use solvent to be tetrahydrofuran (THF), dioxane, chloroform, methylene dichloride, toluene with polymer dissolution;
B) polymers soln is added drop-wise to make polymer precipitation, poor solvent in the poor solvent be normal hexane, methyl alcohol, hexanaphthene, sherwood oil, acetone;
C) object that is used to carry super-hydrophobic polymeric film comprises silicon chip, quartz plate, sheet glass, tinsel, polymeric film.
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| CN100547018C CN100547018C (en) | 2009-10-07 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105789659A (en) * | 2016-04-27 | 2016-07-20 | 北京化工大学 | Alkaline membrane containing cobaltocenium-benzimidazole polymer and preparation method thereof |
| CN111228858A (en) * | 2020-02-17 | 2020-06-05 | 大连理工大学 | Preparation method of super-hydrophobic super-oleophylic nickel-plated carbon fiber |
| CN114891188A (en) * | 2022-04-14 | 2022-08-12 | 香港理工大学深圳研究院 | Conjugated organic metal polymer containing nitroxide free radicals and ferrocene groups, preparation method and application thereof, and composite thermoelectric film |
-
2007
- 2007-04-19 CN CNB2007100985018A patent/CN100547018C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105789659A (en) * | 2016-04-27 | 2016-07-20 | 北京化工大学 | Alkaline membrane containing cobaltocenium-benzimidazole polymer and preparation method thereof |
| CN105789659B (en) * | 2016-04-27 | 2018-05-25 | 北京化工大学 | Alkaline membrane of cation containing cobaltocene-benzimidazole polymer and preparation method thereof |
| CN111228858A (en) * | 2020-02-17 | 2020-06-05 | 大连理工大学 | Preparation method of super-hydrophobic super-oleophylic nickel-plated carbon fiber |
| CN114891188A (en) * | 2022-04-14 | 2022-08-12 | 香港理工大学深圳研究院 | Conjugated organic metal polymer containing nitroxide free radicals and ferrocene groups, preparation method and application thereof, and composite thermoelectric film |
| CN114891188B (en) * | 2022-04-14 | 2023-12-15 | 香港理工大学深圳研究院 | Conjugated organic metal polymer containing nitroxide free radical and ferrocene group, preparation method and application thereof, and composite thermoelectric film |
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