CN103709283B - A kind of cellular porous film of four arm star polymers and preparation method - Google Patents
A kind of cellular porous film of four arm star polymers and preparation method Download PDFInfo
- Publication number
- CN103709283B CN103709283B CN201310689323.1A CN201310689323A CN103709283B CN 103709283 B CN103709283 B CN 103709283B CN 201310689323 A CN201310689323 A CN 201310689323A CN 103709283 B CN103709283 B CN 103709283B
- Authority
- CN
- China
- Prior art keywords
- arm star
- porous film
- component
- methylene dichloride
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The present invention relates to a kind of four arm star-shaped polystyrenes and honeycomb ordered porous film of constructing thereof and preparation method thereof, it is made up of the raw material of following portions by weight: component A (1), vinylbenzene (10-2000), Diisopropyl azodicarboxylate (0.1-50), pimelinketone (10-2000); Wherein: weight fraction and the proportioning of component A are as follows: tetramethylolmethane (1), BDAATC(1-100), methylene dichloride (1-500); The raw material composition of the cellular porous film of the present invention: four arm star-shaped polystyrenes (0.5-10), methylene dichloride (100).Honeycomb ordered porous film of the present invention has the method, and to have preparation technology simple, and solvability is good, and the order of porous membrane is good, and polymer ends has active group to modify further, and cheaper starting materials such as to be easy to get at the feature.
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 method preparing ordered micro structure material noticeable in recent years.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, patterned template, biological medicines.At present filmogen the most common is the polystyrene and multipolymer thereof that are obtained by anionoid polymerization, but anionic polymerisation condition harsh and the monomer that is suitable for less, product category is single, this greatly limits the practical application of cellular porous film.And the development of active free radical polymerization makes the structure of film forming material and chain length control to become possibility, thus have more advantage, for the development of water droplet template provides good opportunity in the morphological structure keeping honeycomb-patterned ordered film.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 reports honeycomb-patterned ordered porous-film prepared by a kind of polystyrene-b-poly N-isopropyl acrylamide (PS-b-PNIPAM) Amphipathilic block polymer, ZL200910098803.4 reports a kind of method being prepared glycosylated and ordered porous membrane by controlled graft polymerization, CN98804709.8 provides the method for the porous-film preparing 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 of being synthesized four arm star-shaped polystyrenes by reversible addion-fragmentation chain transfer (RAFT) radical polymerization, and with this star polymer for filmogen constructs cellular porous film and preparation method, there is the features such as cheap, preparation technology simple, the ordered-form of porous membrane is good.
Object of the present invention realizes by following technical scheme:
A kind of four arm star-shaped polystyrenes are prepared from by the raw material of following portions by weight:
Component A 1
Vinylbenzene 10-2000
Diisopropyl azodicarboxylate 0.1-50
Pimelinketone 10-2000
Wherein: weight fraction and the proportioning of component A 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 component A) in component A.
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 component A) in component A.
Present invention also offers 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 3-48h; reacted rear underpressure distillation; the trithiocarbonate of tetramethylolmethane load, i.e. component A; Stir after component A, vinylbenzene, Diisopropyl azodicarboxylate and pimelinketone proportionally being mixed, at 80-100 DEG C, anaerobic reaction 3-36h, has reacted rear methanol extraction, vacuum-drying, has obtained four arm star-shaped polystyrenes again.
Present invention also offers the cellular porous film of a kind of four arm star polymer, is be prepared from by the raw material of following portions by weight: the arbitrary described four arm star-shaped polystyrene 0.5-10(of claim 1-6 are preferred, and four arm star-shaped polystyrenes get 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.
Present invention also offers the preparation method of the cellular porous film of described four arm star polymer, at stream of nitrogen gas speed 0.1-8L/min, under the condition of humidity 30-90, each raw material being mixed gained solution drips in substrate, namely obtains honeycomb ordered porous film after drying.
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 modify further.
2, this film has the good feature of solvability, can be dissolved in multiple organic solvent.
3, this film has the good feature of order.
Accompanying drawing explanation
The SEM photo of the cellular porous film of Fig. 1: four arm star-shaped polystyrenes.
Embodiment
Describe the solution of the present invention in detail below in conjunction with embodiment and accompanying drawing, 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-PingWang; Li-MinZhao; Wen-ZhiLi; Fabricationofpolymer-hollowsphereoptical-functionalhybri dmaterialviaRAFTpolymerization, Reactive & FunctionalPolymers70 (2010) 35-40.) synthesis.
embodiment one:
The cellular porous film of described four arm star-shaped polystyrene is made up of the raw material of following portions by weight:
Component A 1
Vinylbenzene 250
Diisopropyl azodicarboxylate 0.5
Pimelinketone 250
Wherein: weight fraction and the proportioning of component A 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 as follows: by the tetramethylolmethane of above-mentioned component A, the S of chloride, S '-(a, a '-dimethyl-a "-acetic acid) trithiocarbonate (BDAATC), methylene dichloride stir after being mixed in proportion; and room temperature reaction 48h; reacted rear underpressure distillation, obtains the trithiocarbonate (component A) of tetramethylolmethane load.Stir after again the product of component A, vinylbenzene, Diisopropyl azodicarboxylate and pimelinketone being proportionally mixed in proportion, 100
ounder C, anaerobic reaction 12h, has reacted rear methanol extraction, vacuum-drying, has obtained four arm star-shaped polystyrenes.
The described cellular porous film of four arm star-shaped polystyrenes weight composition and proportioning as follows:
Four arm star-shaped polystyrene 6 methylene dichloride 100
Described cellular porous film and preparation method as follows:
The raw material of said components is mixed, at stream of nitrogen gas speed 4L/min, under the condition of humidity 80, above-mentioned solution is dripped in substrate, after drying, namely obtain honeycomb ordered porous film.Wherein methylene dichloride also can change other solvent such as chloroform, dithiocarbonic anhydride into.
embodiment two:
The cellular porous film of described four arm star-shaped polystyrene is made up of the raw material of following portions by weight:
Component A 1
Vinylbenzene 200
Diisopropyl azodicarboxylate 0.5
Pimelinketone 200
Wherein: weight fraction and the proportioning of component A 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 as follows: by the tetramethylolmethane of above-mentioned component A, the S of chloride, S '-(a, a '-dimethyl-a "-acetic acid) trithiocarbonate (BDAATC), methylene dichloride stir after being mixed in proportion; and room temperature reaction 48h; reacted rear underpressure distillation, obtains the trithiocarbonate (component A) of tetramethylolmethane load.Stir after again the product of component A, vinylbenzene, Diisopropyl azodicarboxylate and pimelinketone being proportionally mixed in proportion, 100
ounder C, anaerobic reaction 12h, has reacted rear methanol extraction, vacuum-drying, has obtained four arm star-shaped polystyrene polymkeric substance.
Described cellular porous film weight composition and proportioning as follows:
Four arm star-shaped polystyrene 4 methylene dichloride 100
Described cellular porous film and preparation method as follows:
The raw material of said components is mixed, at stream of nitrogen gas speed 1.5L/min, under the condition of humidity 80, above-mentioned solution is dripped in substrate, after drying, namely obtain honeycomb ordered porous film.Wherein methylene dichloride also can change other solvent such as chloroform, dithiocarbonic anhydride into.
embodiment three:
The cellular porous film of described four arm star-shaped polystyrene is made up of the raw material of following portions by weight:
Component A 1
Vinylbenzene 300
Diisopropyl azodicarboxylate 0.5
Pimelinketone 300
Wherein: weight fraction and the proportioning of component A 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 as follows: by the tetramethylolmethane of above-mentioned component A, the S of chloride, S '-(a, a '-dimethyl-a "-acetic acid) trithiocarbonate (BDAATC), methylene dichloride stir after being mixed in proportion; and room temperature reaction 48h; reacted rear underpressure distillation, obtains the trithiocarbonate (component A) of tetramethylolmethane load.Stir after again the product of component A, vinylbenzene, Diisopropyl azodicarboxylate and pimelinketone being proportionally mixed in proportion, 100
ounder C, anaerobic reaction 12h, has reacted rear methanol extraction, vacuum-drying, has obtained four arm star-shaped polystyrene polymkeric substance.
Described cellular porous film weight composition and proportioning as follows:
Four arm star-shaped polystyrene 5 methylene dichloride 100
Described cellular porous film and preparation method as follows:
The raw material of said components is mixed, at stream of nitrogen gas speed 2L/min, under the condition of humidity 80, above-mentioned solution is dripped in substrate, after drying, namely obtain honeycomb ordered porous film.Wherein methylene dichloride also can change other solvent such as chloroform, dithiocarbonic anhydride into.
embodiment four:
The cellular porous film of described four arm star-shaped polystyrene is made up of the raw material of following portions by weight:
Component A 1
Vinylbenzene 280
Diisopropyl azodicarboxylate 0.5
Pimelinketone 280
Wherein: weight fraction and the proportioning of component A 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 as follows: by the tetramethylolmethane of above-mentioned component A, the S of chloride, S '-(a, a '-dimethyl-a "-acetic acid) trithiocarbonate (BDAATC), methylene dichloride stir after being mixed in proportion; and room temperature reaction 48h; reacted rear underpressure distillation, obtains the trithiocarbonate (component A) of tetramethylolmethane load.Stir after again the product of component A, vinylbenzene, Diisopropyl azodicarboxylate and pimelinketone being proportionally mixed in proportion, 100
ounder C, anaerobic reaction 12h, has reacted rear methanol extraction, vacuum-drying, has obtained four arm star-shaped polystyrene polymkeric substance.
Described cellular porous film weight composition and proportioning as follows:
Four arm star-shaped polystyrene 7 methylene dichloride 100
Described cellular porous film and preparation method as follows:
The raw material of said components is mixed, at stream of nitrogen gas speed 5L/min, under the condition of humidity 80, above-mentioned solution is dripped in substrate, after drying, namely obtain honeycomb ordered porous film.Wherein methylene dichloride also can change other solvent such as chloroform, dithiocarbonic anhydride into.
Sustentation fund project of the present invention: national natural science fund subsidy project (21203085); Young and middle-aged scientist's scientific research bonus pool (doctor's fund) (BS2011CL011) in Shandong Province.
Claims (5)
1. four arm star-shaped polystyrenes, is characterized in that: be prepared from by the raw material of following portions by weight:
Component A 1
Vinylbenzene 250
Diisopropyl azodicarboxylate 0.5
Pimelinketone 250
Wherein: parts by weight and the proportioning of component A are as follows:
Tetramethylolmethane 1
The S of chloride, S '-(a, a '-dimethyl-a "-acetic acid) trithiocarbonate 10
Methylene dichloride 130.
2. the preparation method of four arm star-shaped polystyrenes according to claim 1, it is characterized in that: by the S of tetramethylolmethane, chloride, S '-(a, a '-dimethyl-a "-acetic acid) trithiocarbonate, methylene dichloride stir after being mixed in proportion; and room temperature reaction 3-48h; reacted rear underpressure distillation, obtains the trithiocarbonate of tetramethylolmethane load, i.e. component A; Stir after component A, vinylbenzene, Diisopropyl azodicarboxylate and pimelinketone proportionally being mixed, at 80-100 DEG C, anaerobic reaction 3-36h, has reacted rear methanol extraction, vacuum-drying, has obtained four arm star-shaped polystyrenes again.
3. the cellular porous film of four arm star polymers, is characterized in that: be prepared from by the raw material of following portions by weight: four arm star-shaped polystyrene 0.5-10 described in claim 1; Methylene dichloride 100.
4. the cellular porous film of four arm star polymers described in claim 3, is characterized in that: methylene dichloride is replaced by chloroform or dithiocarbonic anhydride.
5. the preparation method of the cellular porous film of four arm star polymers described in claim 3, is characterized in that: under the condition of stream of nitrogen gas speed 0.1-8L/min, humidity 30-90, each raw material is mixed gained solution and drip in substrate, after drying and get final product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310689323.1A CN103709283B (en) | 2013-12-17 | 2013-12-17 | A kind of cellular porous film of four arm star polymers and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310689323.1A CN103709283B (en) | 2013-12-17 | 2013-12-17 | A kind of cellular porous film of four arm star polymers and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103709283A CN103709283A (en) | 2014-04-09 |
| CN103709283B true CN103709283B (en) | 2015-12-02 |
Family
ID=50402665
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310689323.1A Expired - Fee Related CN103709283B (en) | 2013-12-17 | 2013-12-17 | A kind of cellular porous film of four arm star polymers and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103709283B (en) |
Families Citing this family (3)
| 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 |
| CN106543321B (en) * | 2015-09-21 | 2018-11-09 | 上海东升新材料有限公司 | The preparation method and its product of a kind of four arms star structure high-efficiency coarse whiting ground dispersant and application |
| CN110022967A (en) * | 2016-11-04 | 2019-07-16 | 香港大学 | Thin property perforated membrane and its manufacturing method entirely |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1869081A (en) * | 2005-05-23 | 2006-11-29 | 中国科学院化学研究所 | Method of one step synthesizing star polymer by free radical polymerization |
| CN102532440A (en) * | 2012-02-07 | 2012-07-04 | 聊城大学 | Honeycomb ordered porous film and preparing method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6596899B1 (en) * | 2000-02-16 | 2003-07-22 | Noveon Ip Holdings Corp. | S,S′BIS-(α, α′-DISUBSTITUTED-α″-ACETIC ACID)- TRITHIOCARBONATES AND DERIVATIVES AS INITIATOR-CHAIN TRANSFER AGENT-TERMINATOR FOR CONTROLLED RADICAL POLYMERIZATIONS AND THE PROCESS FOR MAKING THE SAME |
-
2013
- 2013-12-17 CN CN201310689323.1A patent/CN103709283B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1869081A (en) * | 2005-05-23 | 2006-11-29 | 中国科学院化学研究所 | Method of one step synthesizing star polymer by free radical polymerization |
| CN102532440A (en) * | 2012-02-07 | 2012-07-04 | 聊城大学 | Honeycomb ordered porous film and preparing method |
Non-Patent Citations (2)
| Title |
|---|
| S,S’-二（a, a’-甲基-a"-乙酸）三硫代碳酯存在下的热聚合反应及光聚合反应;冉蓉等;《石油化工》;20061130;第35卷(第3期);第226-230页 * |
| 以季戊四醇为核的多臂星形链转移剂的合成及表征;陈卫星等;《高分子材料科学与工程》;20080930;第24卷(第9期);第56-59页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103709283A (en) | 2014-04-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Raravikar et al. | Synthesis and characterization of thickness-aligned carbon nanotube− polymer composite films | |
| Friebe et al. | Controlled pore functionalization of poly (ethylene terephthalate) track-etched membranes via surface-initiated atom transfer radical polymerization | |
| Zhang et al. | Enhancement of esterification conversion using novel composite catalytically active pervaporation membranes | |
| He et al. | Synthesis of cagelike polymer microspheres with hollow core/porous shell structures by self-assembly of latex particles at the emulsion droplet interface | |
| Zhao et al. | Towards directional assembly of hierarchical structures: aniline oligomers as the model precursors | |
| Rahy et al. | Polyaniline nanofiber synthesis by co-use of ammonium peroxydisulfate and sodium hypochlorite | |
| CN101824118A (en) | Porous polymer nanoparticles and preparation method thereof | |
| Hashidzume et al. | Macroscopic self-assembly based on molecular recognition: effect of linkage between aromatics and the polyacrylamide gel scaffold, amide versus ester | |
| CN103709283B (en) | A kind of cellular porous film of four arm star polymers and preparation method | |
| CN103087243B (en) | Porous polymer hollow micro-capsule and preparation method and application thereof | |
| Liu et al. | Surface molecular imprinted layer-by-layer film attached to a porous membrane for selective filtration | |
| Roth et al. | UCST-driven self-assembly and crosslinking of diblock copolymer micelles | |
| Heng et al. | Ordered honeycomb structural interfaces for anticancer cells growth | |
| Oh et al. | Semipermeable microcapsules with a block-polymer-templated nanoporous membrane | |
| CN102532440B (en) | Honeycomb ordered porous film and preparing method | |
| CN102161768A (en) | Polysiloxane-polyphenyl ether crosslinked block copolymer and preparation method and use thereof | |
| Khalil et al. | Enabling solution processable COFs through suppression of precipitation during solvothermal synthesis | |
| WO2013191130A1 (en) | Composite of polymer and tungstic acid and/or molybdic acid | |
| Li et al. | Porous polymer films with size-tunable surface pores | |
| CN105801921B (en) | A kind of cellulose esterification derivative ordered porous membrane material and preparation method thereof | |
| CN102731738A (en) | Polyhedral oligomeric silsesquioxane (POSS) based patterned nano microsphere and preparation method thereof | |
| Kadla et al. | Micropatterned thin film honeycomb materials from regiospecifically modified cellulose | |
| Jin et al. | Fabrication of pill-shaped polyimide aerogel particles using microfluidic flows | |
| Watanabe et al. | Multilayer poly (ionic liquid) microcapsules prepared by sequential phase separation and subsequent photopolymerization in ternary emulsion droplets | |
| Guo et al. | Protein valves formed through click-reaction grafting of poly (N-isopropylacrylamide) onto electrospun poly (2, 6-dimethyl-1, 4-phenylene oxide) fibrous membranes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20151202 Termination date: 20161217 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |