CN103709283A - Honeycomb porous membrane made of four-arm star-shaped polymer and preparation method of honeycomb porous membrane - Google Patents
Honeycomb porous membrane made of four-arm star-shaped polymer and preparation method of honeycomb porous membrane Download PDFInfo
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Abstract
The invention relates to four-arm star-shaped polystyrene, a honeycomb porous membrane made of the same and a preparation method of the honeycomb porous membrane. The four-arm star-shaped polystyrene is prepared from the following raw materials in parts by weight: 1 part of component A, 10-2000 parts of styrene, 0.1-50 parts of azobisisobutyronitrile and 10-2000 parts of cyclohexanone, wherein the component A comprises the following ingredients in parts by weight: 1 part of pentaerythritol, 1-100 parts of BDAATC and 1-500 parts of dichloromethane. The honeycomb porous membrane provided by the invention is prepared from the raw materials: 0.5-10 parts of four-arm star-shaped polystyrene and 100 parts of dichloromethane. The honeycomb porous membrane provided by the invention has the characteristics of simplicity in preparation process, good solubility and orderliness and the like; the tail end of the polymer is provided with active groups so that the further modification can be carried out; the raw materials are cheap and are easy to obtain.
Description
Technical field
The present invention relates to the cellular porous film of a kind of four arm star polymer and preparation method.
Background technology
Water droplet template is a kind of noticeable in recent years method of preparing orderly fine structure material.Prepared cellular porous film has very important application prospect in fields such as micro-container and microreactor, optical material, cell culturing bracket, super hydrophobic surface, patterning template, biological medicines.At present the most common filmogen is polystyrene and the multipolymer thereof obtaining by anionoid polymerization, but the harsh and applicable monomer of anionic polymerisation condition is less, and product category is single, and this has greatly limited the practical application of cellular porous film.And the development of active free radical polymerization is controlled the structure of film forming material and chain length to become possibility, thereby keeping aspect the morphological structure of honeycomb-patterned ordered film having more advantage, for the development of water droplet template provides good opportunity.Up to now, star polymer, hyperbranched polymer, line polymer, rod-line polymkeric substance, metal and inorganic nano-particle and even small molecules are all used to prepare honeycomb-patterned ordered porous-film.CN201210025266.2 has reported honeycomb-patterned ordered porous-film prepared by a kind of polystyrene-b-poly N-isopropyl acrylamide (PS-b-PNIPAM) Amphipathilic block polymer, ZL200910098803.4 has reported a kind of method of preparing glycosylated and ordered porous membrane by controlled graft polymerization, CN98804709.8 provides the method for preparing the porous-film of surface modification with perfluorocarbon copolymer, CN00800175.8 provides a kind of polyolefin micro porous polyolefin membrane and manufacture method thereof, ZL200810061711.4 provides a kind of preparation method and its usage of glycosylated and ordered porous membrane, CN200410047286.5 provides hydrophilization porous-film and preparation method thereof.This patent will provide the cellular porous film of a kind of four arm star polymer and preparation method, and it is simple that the method has preparation technology, and porous membrane order is good, and polymer ends is with features such as active groups.
Summary of the invention
The object of the present invention is to provide a kind of method that shifts the synthetic four arm star-shaped polystyrenes of (RAFT) radical polymerization by reversible addition-fracture chain, and take this star polymer and construct cellular porous film and preparation method as filmogen, there is the features such as cheap, preparation technology simple, the ordered-form of porous membrane is good.
Object of the present invention can be achieved through the following technical solutions:
Four arm star-shaped polystyrenes are that the raw material by following portions by weight is prepared from:
A component 1
Vinylbenzene 10-2000
Diisopropyl azodicarboxylate 0.1-50
Pimelinketone 10-2000
Wherein: weight fraction and the proportioning of A component are as follows:
Tetramethylolmethane 1
The S of chloride, S '-(a, a '-dimethyl-a "-acetic acid) trithiocarbonate (BDAATC) 1-100
Methylene dichloride 1-500.
Foregoing four arm star-shaped polystyrenes, preferred scheme is: vinylbenzene accounts for 10-2000 weight part (preferred, vinylbenzene accounts for 250 weight parts).
Foregoing four arm star-shaped polystyrenes, preferred scheme is: Diisopropyl azodicarboxylate accounts for 0.1-50 weight part (preferred, Diisopropyl azodicarboxylate accounts for 0.5 weight part).
Foregoing four arm star-shaped polystyrenes, preferred scheme is: pimelinketone accounts for 10-2000 weight part (preferred, pimelinketone accounts for 250 weight parts).
Foregoing four arm star-shaped polystyrenes, preferred scheme is: the S of chloride, S '-(a, a '-dimethyl-a "-acetic acid) trithiocarbonate accounts for 1-100 weight part (preferred; the S of chloride; S '-(a, a '-dimethyl-a "-acetic acid) trithiocarbonate accounts for 10 weight parts in A component) in A component.
Foregoing four arm star-shaped polystyrenes, preferred scheme is: methylene dichloride accounts for 1-500 weight part (preferred, methylene dichloride accounts for 130 weight parts in A component) in A component.
The present invention also provides the preparation method of foregoing four arm star-shaped polystyrenes: by the S of tetramethylolmethane, chloride, S '-(a, a '-dimethyl-a "-acetic acid) trithiocarbonate (BDAATC), methylene dichloride stir after being mixed in proportion; room temperature reaction 3-48 h; reacted rear underpressure distillation; the trithiocarbonate of tetramethylolmethane load, i.e. component A; After component A, vinylbenzene, Diisopropyl azodicarboxylate and pimelinketone proportionally being mixed, stir, anaerobic reaction 3-36 h, react rear use methanol extraction at 80-100 ℃ again, and vacuum-drying, obtains four arm star-shaped polystyrenes.
The present invention also provides a kind of four arm star polymer cellular porous film, is that the raw material by following portions by weight is prepared from: the arbitrary described four arm star-shaped polystyrene 0.5-10(of claim 1-6 are preferred, and four arm star-shaped polystyrenes are got 0.5-10 part); Methylene dichloride 100.
The cellular porous film of four arm star polymer noted earlier, wherein methylene dichloride is replaced by chloroform or dithiocarbonic anhydride.
The present invention also provides the preparation method of the cellular porous film of described four arm star polymer, at stream of nitrogen gas speed 0.1-8 L/min, under the condition of humidity 30-90, each raw material is mixed to gained solution and drip in substrate, after being dried, obtain honeycomb ordered porous film.
The cellular porous film of the present invention compared to existing technology tool has the following advantages:
1, the filmogen end of this film has active group, can further modify.
2, this film has the advantages that solvability is good, can be dissolved in multiple organic solvent.
3, this film has the advantages that order is good.
Accompanying drawing explanation
Fig. 1: the SEM photo of the cellular porous film of four arm star-shaped polystyrenes.
Embodiment
Below in conjunction with embodiment and accompanying drawing, describe the solution of the present invention in detail, but protection domain is not by this restriction.Raw materials used if Diisopropyl azodicarboxylate, vinylbenzene, pimelinketone, tetramethylolmethane, methylene dichloride etc. are purchased from Aladdin reagent company limited in embodiment.
The S of chloride, S '-(a, a '-dimethyl-a "-acetic acid) trithiocarbonate (BDAATC) is according to document 1(document 1:Li-Ping Wang; Li-Min Zhao; Wen-Zhi Li; Fabrication of polymer-hollow sphere optical-functional hybrid material via RAFT polymerization, Reactive & Functional Polymers 70 (2010) 35-40.) synthetic.
embodiment mono-:
The cellular porous film of described four arm star-shaped polystyrene is comprised of the raw material of following portions by weight:
A component 1
Vinylbenzene 250
Diisopropyl azodicarboxylate 0.5
Pimelinketone 250
Wherein: weight fraction and the proportioning of A component are as follows:
Tetramethylolmethane 1
The S of chloride, S '-(a, a '-dimethyl-a "-acetic acid) trithiocarbonate (BDAATC) 10
Methylene dichloride 130
Described four arm star-shaped polystyrene polymkeric substance and preparation method are as follows: by the S of the tetramethylolmethane of above-mentioned A component, chloride, S '-(a, a '-dimethyl-a "-acetic acid) trithiocarbonate (BDAATC), methylene dichloride stir after being mixed in proportion; and room temperature reaction 48 h; reacted rear underpressure distillation, obtain the trithiocarbonate (component A) of tetramethylolmethane load.After again the product of A component, vinylbenzene, Diisopropyl azodicarboxylate and pimelinketone being proportionally mixed in proportion, stir, 100
ounder C, anaerobic is reacted 12 h, has reacted rear with methanol extraction, and vacuum-drying, obtains four arm star-shaped polystyrenes.
Weight composition and the proportioning of the described cellular porous film of four arm star-shaped polystyrenes are as follows:
Four arm star-shaped polystyrene 6 methylene dichloride 100
Described cellular porous film and preparation method are as follows:
The raw material of said components is mixed, at stream of nitrogen gas speed 4 L/min, under the condition of humidity 80, above-mentioned solution is dripped in substrate, after being dried, obtain honeycomb ordered porous film.Wherein methylene dichloride also can change other solvents such as chloroform, dithiocarbonic anhydride into.
embodiment bis-:
The cellular porous film of described four arm star-shaped polystyrene is comprised of the raw material of following portions by weight:
A component 1
Vinylbenzene 200
Diisopropyl azodicarboxylate 0.5
Pimelinketone 200
Wherein: weight fraction and the proportioning of A component are as follows:
Tetramethylolmethane 1
The S of chloride, S '-(a, a '-dimethyl-a "-acetic acid) trithiocarbonate (BDAATC) 13
Methylene dichloride 150
Described four arm star-shaped polystyrene polymkeric substance and preparation method are as follows: by the S of the tetramethylolmethane of above-mentioned A component, chloride, S '-(a, a '-dimethyl-a "-acetic acid) trithiocarbonate (BDAATC), methylene dichloride stir after being mixed in proportion; and room temperature reaction 48 h; reacted rear underpressure distillation, obtain the trithiocarbonate (component A) of tetramethylolmethane load.After again the product of A component, vinylbenzene, Diisopropyl azodicarboxylate and pimelinketone being proportionally mixed in proportion, stir, 100
ounder C, anaerobic is reacted 12 h, has reacted rear with methanol extraction, and vacuum-drying, obtains four arm star-shaped polystyrene polymkeric substance.
Weight composition and the proportioning of described cellular porous film are as follows:
Four arm star-shaped polystyrene 4 methylene dichloride 100
Described cellular porous film and preparation method are as follows:
The raw material of said components is mixed, at stream of nitrogen gas speed 1.5 L/min, under the condition of humidity 80, above-mentioned solution is dripped in substrate, after being dried, obtain honeycomb ordered porous film.Wherein methylene dichloride also can change other solvents such as chloroform, dithiocarbonic anhydride into.
embodiment tri-:
The cellular porous film of described four arm star-shaped polystyrene is comprised of the raw material of following portions by weight:
A component 1
Vinylbenzene 300
Diisopropyl azodicarboxylate 0.5
Pimelinketone 300
Wherein: weight fraction and the proportioning of A component are as follows:
Tetramethylolmethane 1
The S of chloride, S '-(a, a '-dimethyl-a "-acetic acid) trithiocarbonate (BDAATC) 15
Methylene dichloride 180
Described four arm star-shaped polystyrene polymkeric substance and preparation method are as follows: by the S of the tetramethylolmethane of above-mentioned A component, chloride, S '-(a, a '-dimethyl-a "-acetic acid) trithiocarbonate (BDAATC), methylene dichloride stir after being mixed in proportion; and room temperature reaction 48 h; reacted rear underpressure distillation, obtain the trithiocarbonate (component A) of tetramethylolmethane load.After again the product of A component, vinylbenzene, Diisopropyl azodicarboxylate and pimelinketone being proportionally mixed in proportion, stir, 100
ounder C, anaerobic is reacted 12 h, has reacted rear with methanol extraction, and vacuum-drying, obtains four arm star-shaped polystyrene polymkeric substance.
Weight composition and the proportioning of described cellular porous film are as follows:
Four arm star-shaped polystyrene 5 methylene dichloride 100
Described cellular porous film and preparation method are as follows:
The raw material of said components is mixed, at stream of nitrogen gas speed 2 L/min, under the condition of humidity 80, above-mentioned solution is dripped in substrate, after being dried, obtain honeycomb ordered porous film.Wherein methylene dichloride also can change other solvents such as chloroform, dithiocarbonic anhydride into.
embodiment tetra-:
The cellular porous film of described four arm star-shaped polystyrene is comprised of the raw material of following portions by weight:
A component 1
Vinylbenzene 280
Diisopropyl azodicarboxylate 0.5
Pimelinketone 280
Wherein: weight fraction and the proportioning of A component are as follows:
Tetramethylolmethane 1
The S of chloride, S '-(a, a '-dimethyl-a "-acetic acid) trithiocarbonate (BDAATC) 10
Methylene dichloride 120
Described four arm star-shaped polystyrene polymkeric substance and preparation method are as follows: by the S of the tetramethylolmethane of above-mentioned A component, chloride, S '-(a, a '-dimethyl-a "-acetic acid) trithiocarbonate (BDAATC), methylene dichloride stir after being mixed in proportion; and room temperature reaction 48 h; reacted rear underpressure distillation, obtain the trithiocarbonate (component A) of tetramethylolmethane load.After again the product of A component, vinylbenzene, Diisopropyl azodicarboxylate and pimelinketone being proportionally mixed in proportion, stir, 100
ounder C, anaerobic is reacted 12 h, has reacted rear with methanol extraction, and vacuum-drying, obtains four arm star-shaped polystyrene polymkeric substance.
Weight composition and the proportioning of described cellular porous film are as follows:
Four arm star-shaped polystyrene 7 methylene dichloride 100
Described cellular porous film and preparation method are as follows:
The raw material of said components is mixed, at stream of nitrogen gas speed 5 L/min, under the condition of humidity 80, above-mentioned solution is dripped in substrate, after being dried, obtain honeycomb ordered porous film.Wherein methylene dichloride also can change other solvents such as chloroform, dithiocarbonic anhydride into.
Sustentation fund project of the present invention: national natural science fund subsidy project (21203085); The young and middle-aged scientist's scientific research bonus pool in Shandong Province (doctor's fund) (BS2011CL011).
Claims (10)
1. four arm star-shaped polystyrenes, is characterized in that: be that raw material by following portions by weight is prepared from:
A component 1
Vinylbenzene 10-2000
Diisopropyl azodicarboxylate 0.1-50
Pimelinketone 10-2000
Wherein: weight fraction and the proportioning of A component are as follows:
Tetramethylolmethane 1
The S of chloride, S '-(a, a '-dimethyl-a "-acetic acid) trithiocarbonate (BDAATC) 1-100
Methylene dichloride 1-500.
2. a kind of four arm star-shaped polystyrenes according to claim 1, is characterized in that: vinylbenzene accounts for 10-2000 weight part (preferred, vinylbenzene accounts for 250 weight parts).
3. a kind of four arm star-shaped polystyrenes according to claim 1, is characterized in that: Diisopropyl azodicarboxylate accounts for 1.1-50 weight part (preferred, Diisopropyl azodicarboxylate accounts for 0.5 weight part).
4. a kind of four arm star-shaped polystyrenes according to claim 1, is characterized in that: pimelinketone accounts for 10-2000 weight part (preferred, pimelinketone accounts for 250 weight parts).
5. a kind of four arm star-shaped polystyrenes according to claim 1, it is characterized in that: the S of chloride, S '-(a, a '-dimethyl-a "-acetic acid) trithiocarbonate accounts for 1-100 weight part (preferred; the S of chloride; S '-(a, a '-dimethyl-a "-acetic acid) trithiocarbonate accounts for 10 weight parts in A component) in A component.
6. a kind of four arm star-shaped polystyrenes according to claim 1, is characterized in that: methylene dichloride accounts for 1-500 weight part (preferred, methylene dichloride accounts for 130 weight parts in A component) in A component.
7. according to the preparation method of the arbitrary described four arm star-shaped polystyrenes of claim 1-6, it is characterized in that: by the S of tetramethylolmethane, chloride, S '-(a, a '-dimethyl-a "-acetic acid) trithiocarbonate (BDAATC), methylene dichloride stir after being mixed in proportion; and room temperature reaction 3-48 h; reacted rear underpressure distillation, obtains the trithiocarbonate of tetramethylolmethane load, i.e. component A; After component A, vinylbenzene, Diisopropyl azodicarboxylate and pimelinketone proportionally being mixed, stir, anaerobic reaction 3-36 h, react rear use methanol extraction at 80-100 ℃ again, and vacuum-drying, obtains four arm star-shaped polystyrenes.
8. the cellular porous film of four arm star polymers, is characterized in that: be that raw material by following portions by weight is prepared from: the arbitrary described four arm star-shaped polystyrene 0.5-10(of claim 1-6 are preferred, and four arm star-shaped polystyrenes are got 0.5-10 part); Methylene dichloride 100.
9. the cellular porous film of four arm star polymers described in claim 8, is characterized in that: wherein methylene dichloride is replaced by chloroform or dithiocarbonic anhydride.
10. the preparation method of the cellular porous film of four arm star polymers described in claim 8-9, it is characterized in that: at stream of nitrogen gas speed 0.1-8 L/min, under the condition of humidity 30-90, each raw material is mixed to gained solution and drip in substrate, after being dried, obtain honeycomb ordered porous film.
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Cited By (3)
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| CN104031189A (en) * | 2014-06-27 | 2014-09-10 | 聊城大学 | Six-arm star-shaped polymer porous membrane and preparation method thereof |
| CN106543321A (en) * | 2015-09-21 | 2017-03-29 | 上海东升新材料有限公司 | A kind of preparation method of four arms star structure high-efficiency coarse whiting ground dispersant and its product and application |
| WO2018082024A1 (en) * | 2016-11-04 | 2018-05-11 | The University Of Hong Kong | Omniphobic porous membrane and methods for preparing the same |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104031189A (en) * | 2014-06-27 | 2014-09-10 | 聊城大学 | Six-arm star-shaped polymer porous membrane and preparation method thereof |
| CN106543321A (en) * | 2015-09-21 | 2017-03-29 | 上海东升新材料有限公司 | A kind of preparation method of four arms star structure high-efficiency coarse whiting ground dispersant and its product and application |
| WO2018082024A1 (en) * | 2016-11-04 | 2018-05-11 | The University Of Hong Kong | Omniphobic porous membrane and methods for preparing the same |
| CN110022967A (en) * | 2016-11-04 | 2019-07-16 | 香港大学 | Thin property perforated membrane and its manufacturing method entirely |
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