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
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- 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
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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.
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---|
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 * |
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