CN1702088A - Fluorine-containing block copolymer and its preparation process and use thereof - Google Patents

Fluorine-containing block copolymer and its preparation process and use thereof Download PDF

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CN1702088A
CN1702088A CN 200510026512 CN200510026512A CN1702088A CN 1702088 A CN1702088 A CN 1702088A CN 200510026512 CN200510026512 CN 200510026512 CN 200510026512 A CN200510026512 A CN 200510026512A CN 1702088 A CN1702088 A CN 1702088A
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parts
weight
block copolymer
fluorinated block
bpy
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CN1332992C (en
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胡春圃
董擎之
刘涛
王孜
杨亚军
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China Petroleum and Chemical Corp
East China University of Science and Technology
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China Petroleum and Chemical Corp
East China University of Science and Technology
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Abstract

The invention discloses a fluorine block copolymer and its preparation and application. The invention is a two-block copolymer of phenylethene-acrylic nitrile random copolymer and fluorine monomer MAA-2-carbethoxy. The invention can be used as stabilizer in SCCO2. The structure is Rf=-(CH2)2OC9F17. Rf=-(CH2)2OC9F17.

Description

Fluorinated block copolymer and its production and application
Technical field
The present invention relates to a kind of fluorinated block copolymer, relate in particular to a kind of supercritical CO that is used for 2The fluorinated block copolymer of the stablizer in the middle polyacrylonitrile preparation process.
Background technology
Supercritical CO 2(SCCO 2) feature the most excellent in polyreaction is: as have diffustivity as gas; Have density, can make a lot of compound solvations as liquid.
Because SCCO 2Low viscosity, reduced the solvent cage effect during decomposition of initiator, quickened reaction process; SCCO 2Environmentally friendly, and alternative a large amount of conventional solvent; CO 2In the occurring in nature enormous amount; CO 2Stagnation point is low, is easy to get, and as renewable behind the solvent, thereby avoids aggravation to Greenhouse effect; CO 2Be a kind of physical environment gas, can from reaction medium, separate, make the polymkeric substance seasoning, save the desolventizing process of high energy consumption by release; SCCO 2Another key property in polymerization process is plasticizing, and this causes the Tg of superpolymer to reduce, and the interpolation component is penetrated in the superpolymer, and certain development space is arranged in modifying orlon; The plastifying state of the height of polymkeric substance has improved the monomer rate of diffusion again, thereby has improved rate of polymerization; Plasticizing rate can be used SCCO 2Pressure, temperature regulation, the plasticizing of superpolymer also can reduce the viscosity of its fusing point and solution, and influences the morphological structure of superpolymer.
SCCO 2As the radical polymerization of the green solvent of polyreaction at vinylbenzene, vinylformic acid and methacrylic acid, the cationoid polymerisation of isotactic polybutene, polyvinyl ether and polystyrene has had report in the metal transfer catalyzed polymerization of norbornylene and epoxy compounds etc.Because polymkeric substance is at SCCO 2In insoluble, need to adopt suitable tensio-active agent at SCCO 2In as stablizer, the synthetic or screening of stablizer is one of key issue of this research.
In the today to the environmental protection pay attention to day by day, the VOS that uses in the production pollution to environment is more and more recognized in acrylic fiber production process industry.In the searching process of the solvent that polyreaction is suitable for, scientist turns to green solvent-supercritical CO with attention 2(SCCO 2).
Because polyacrylonitrile insoluble in SCCO2, need to adopt suitable tensio-active agent in SCCO2 as stablizer, the synthetic or screening of tensio-active agent is one of key issue of this research.According to foreign literature, some unformed fluorine-containing polymer and polysiloxane and derivative thereof successfully are applied to be insoluble in the heterogeneous polymerization process of superpolymer of CO2.
Macromolecules 2000,33, and in 1565 documents, DeSimone proposes, at SCCO 2Use the PS-PFOA multipolymer as stablizer in the dispersion polymerization of polyacrylonitrile, stabilizing agent dosage is big (30% monomer mass) too.Because the anchor section of existing stablizer is pure polystyrene, with the consistency of polyacrylonitrile and bad, need add at least that 15%wt just produces effect, and need very big pressure (38MPa), even under such pressure, the stablizer of 10%wt still can not obtain the spheroidal particle of regular shape.
Summary of the invention
The technical issues that need to address of the present invention are to disclose a kind of fluorinated block copolymer and its production and application, to overcome the above-mentioned defective that prior art exists.
Fluorinated block copolymer of the present invention is the Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock of a kind of styrene-acrylonitrile random copolymers and fluorochemical monomer methacrylic acid-2-(perfluorinated nonene oxygen base) ethyl ester, and its structure approaches polyacrylonitrile, and structure fragment is as follows:
Figure A20051002651200051
Rf＝-(CH 2) 2OC 9F 17
Wherein: n=50～90, m=20～30; Molecular weight is 14000～21000;
Fluorinated block copolymer of the present invention can adopt magnetic nuclear resonance method to characterize.
1H NMR characterizes and uses Bruker 500MHz nuclear magnetic resonance analyser, uses deuterochloroform (CDCl 3) be solvent, TMS is interior mark.GPC characterizes and uses Tianjin, island SCL-10A VP gel permeation chromatograph, and PS (Showa Denko K. K's product) is a standard specimen, N, and N '-dimethyl formamide (DMF) is a moving phase, 40 ℃ of column temperatures, flow 0.722ml/min.
Said fluorinated block copolymer can adopt the method for atom transfer radical polymerization to be prepared, and specifically comprises the steps:
(1) preparation of macromole evocating agent: with part bpy and Catalysts Cu Br under nitrogen protection, react down in 90～110 ℃ with monomer styrene, vinyl cyanide and initiator, reaction times is 4～10 hours, add tetrahydrofuran (THF) then, macromole evocating agent is collected in ultrasonic dispersing 10～30min dissolving then from reaction product;
Said initiator is selected from a kind of in alpha-brominated ethyl isobutyrate, bromine ethylbenzene, the alpha-brominated propionitrile;
The chemical name of said part bpy is 2, and 2 '-dipyridyl can adopt the commercially available prod, as the product of Shanghai traditional Chinese medicines reagent company;
The parts by weight of bpy are 1.72～3.83 parts;
The parts by weight of CuBr are 0.52～1.17 part;
Cinnamic parts by weight are 72.41～69.23 parts;
The parts by weight of vinyl cyanide are 23.91～22.56 parts;
The parts by weight of initiator are 1.44～3.20 parts.
(2) preparation of fluorinated block copolymer: with the macromole evocating agent of part bpy, Catalysts Cu Br and step (1) under nitrogen protection; with phenylfluoroform and/or tetrahydrofuran solvent; react with fluorochemical monomer methacrylic acid-2-(perfluorinated nonene oxygen base) ethyl ester; temperature of reaction is 80～100 ℃; reaction times is 16～100 hours, collects the fluorinated block copolymer of white powder state then from reaction product.
The parts by weight of bpy are 0.95～2.38 part;
The parts by weight of CuBr are 0.29～0.73 part;
The parts by weight of macromole evocating agent are 10.50～33.01 parts;
The parts by weight of fluorochemical monomer methacrylic acid-2-(perfluorinated nonene oxygen base) ethyl ester are 64.19～88.21 parts.
Said fluorochemical monomer methacrylic acid-2-(perfluorinated nonene oxygen base) ethyl ester can adopt Ishikawa N.Org Synth Chem (Japan) 1981; 39:52. the document disclosed method is prepared;
Fluorinated block copolymer of the present invention can be used as SCCO 2The stablizer that uses in the middle polyacrylonitrile dispersion polymerization, stabilizing agent dosage only is 10% of an acrylonitrile monemer quality, just can reach the ideal polymerization effect.
SCCO 2The middle diffuse-aggregate method of polyacrylonitrile is reported in many documents to some extent, adopts fluorinated block copolymer of the present invention as SCCO 2In use in the polyacrylonitrile dispersion polymerization stablizer the time, basic skills is identical with routine, fluorinated block copolymer simply can be added the precipitation polymerization system: after adding magnetic stir bar, initiator, vinyl cyanide and stablizer in the stainless steel autoclave, sealing, place cryosel to bathe fully cooling reactor after emptying finishes, feed CO 2After still is immersed in 65 ℃ of waters bath with thermostatic control reaction 20 hours.
The present invention adopts the method for atom transfer radical polymerization to prepare said fluorinated block copolymer, the applicable monomer limitation that has overcome common use initiation-transfer-termination tech and anionoid polymerization greatly with and reaction conditions require very harsh shortcoming.
The present invention utilizes vinyl cyanide in supercritical co the dispersion polymerization of prepared fluorinated block copolymer as stablizer, owing to introduced acrylonitrile unit, therefore and the consistency of polyacrylonitrile than external prior art use stablizer better, time just can reach stabilising effect preferably at low concentration (10%) and lower pressure (20MPa).Owing to added stablizer, reaction system has become dispersion polymerization by precipitation polymerization, when lower initiator concentration (0.5%) and lower monomer concentration (0.1g/ml), just can obtain quite high transformation efficiency (about 60%) and molecular weight (surpassing 52700).
Description of drawings
Fig. 1 is the electromicroscopic photograph of the precipitation polymerization product of vinyl cyanide in supercritical co.
Fig. 2 has added the electromicroscopic photograph of fluorinated block copolymer as the dispersion polymerization product of vinyl cyanide in supercritical co of stablizer.
Embodiment
Embodiment 1
The preparation method of fluorinated block copolymer:
The preparation of macromole evocating agent (SAN-1): (SAN-1) 20ml single port flask is put into to vacuumize after the magnetic stir bar and is removed moisture and air, feeds nitrogen again, three times repeatedly.Add part bpy 1.495 * 10 -1G, Catalysts Cu Br 4.56 * 10 -2Behind the g, vacuumize logical nitrogen once more, keep after three times positive pressure of nitrogen (40mmHg) back to seal repeatedly with rubber tubing.Add monomer 3mL vinylbenzene and 1.1mL vinyl cyanide with syringe, add the alpha-brominated ethyl isobutyrate of initiator 94 μ L again, at last flask is placed 100 ℃ of oil bath reactions 4 hours.Reaction finishes the back and takes out flask, adds the 5mL tetrahydrofuran (THF) while hot, and ultrasonic dispersing 20min dissolving is poured solution in the 100mL normal hexane into and is settled out polymkeric substance, and vacuum-drying at room temperature is to constant weight after the filtration.After calculating transformation efficiency, once more product is dissolved in the 40mL tetrahydrofuran (THF), through Al 2O 3After copper salt catalyst is removed in post absorption, vacuum-drying under the room temperature once more.Final product is a white powder.
The preparation of fluorinated block copolymer (F1-MK2):: 20ml single port flask is put into to vacuumize after the magnetic stir bar and is removed moisture and air, feeds nitrogen again, three times repeatedly.Add part bpy 4.672 * 10 -2G, Catalysts Cu Br 1.424 * 10 -2Behind g and the macromole evocating agent SAN-1 0.5g, vacuumize logical nitrogen once more, keep after three times positive pressure of nitrogen (40mmHg) back to seal repeatedly with rubber tubing.Add solvent 3mL phenylfluoroform and 3mL tetrahydrofuran (THF) with syringe, add monomer methacrylic acid-2-(perfluorinated nonene oxygen base) ethyl ester (FNEMA) 2mL again, at last flask is placed 90 ℃ of oil bath reactions 36 hours.Reaction finishes the back and takes out flask, and solution is poured in the 80mL methyl alcohol and is settled out polymkeric substance, and vacuum-drying at room temperature is to constant weight after the filtration.After calculating transformation efficiency, once more product is dissolved in the 30mL tetrahydrofuran (THF), through Al 2O 3After copper salt catalyst is removed in post absorption, vacuum-drying under the room temperature once more.Final product is a white powder.
Below be the nuclear-magnetism characterization data of fluorinated block copolymer:
The peak ownership of chemical shift 6.7ppm and 7.1ppm is the aromatic ring proton peak on the vinylbenzene, 0.9ppm the peak of locating can belong to the methyl on the alpha-brominated ethyl isobutyrate, 1.2ppm be methylene radical and methyne on vinylbenzene and the vinyl cyanide random polymerization chain to 2.5ppm place ownership, 4.4ppm place ownership is the oxyethyl group on the fluorochemical monomer.
Embodiment 2
Use of vinyl cyanide in supercritical co the dispersion polymerization of the fluorinated block copolymer of embodiment 1 as stablizer:
(the macromole evocating agent molecular weight is about 5000 to add magnetic stir bar, initiator A IBN 0.02g, vinyl cyanide 2.5mL and stablizer (5K/16K) in the 20mL stainless steel autoclave, the fluorine-containing groups molecular weight is about 16000) behind the 0.2g, sealing slowly feeds CO 2Air in the removal system.Emptying finishes, and places cryosel to bathe fully cooling reactor, feeds CO 2After still is immersed in 65 ℃ of waters bath with thermostatic control reaction 20 hours (this moment, pressure was 20 ± 0.5MPa).After reaction finishes, place cryosel to bathe fully cooling once more reactor, to pressure be 5MPa when following, open valve and slowly discharge CO 2During discharging, scrape product with pocket knife earlier, clean in the still with DMF, last weighing reactor calculates transformation efficiency cleaning the of poor quality of front and back.Final product is a white powder.
Obtained ideal rule polyacrylonitrile particle.Its electromicroscopic photograph is seen Fig. 2.
The comparative example 1
Adopt precipitation polymerization to prepare polyacrylonitrile, its electromicroscopic photograph is seen Fig. 1.
By embodiment 2 and comparative example's 1 electromicroscopic photograph as seen, the particle shape of the precipitation polymerization product in the document is irregular, and it is very serious to reunite, and does not see the size of particle, and the diffuse-aggregate spheroidal particle of rule of shape that obtained of example 2.

Claims (6)

1. a fluorinated block copolymer is characterized in that, is the Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock of a kind of styrene-acrylonitrile random copolymers and fluorochemical monomer methacrylic acid-2-(perfluorinated nonene oxygen base) ethyl ester, and structure fragment is as follows:
Rf＝-(CH 2) 2OC 0F 17
Wherein: n=50～90, m=20～30; Molecular weight is 14000～21000.
2. the preparation method of fluorinated block copolymer according to claim 1 is characterized in that, comprises the steps:
(1) preparation of macromole evocating agent: with part bpy and Catalysts Cu Br under nitrogen protection, react down in 90～110 ℃ with monomer styrene, vinyl cyanide and initiator, reaction times is 4～10 hours, add tetrahydrofuran (THF) then, macromole evocating agent is collected in ultrasonic dispersing 10～30min dissolving then from reaction product;
(2) preparation of fluorinated block copolymer: with the macromole evocating agent of part bpy, Catalysts Cu Br and step (1) under nitrogen protection; with phenylfluoroform and/or tetrahydrofuran solvent; react with fluorochemical monomer methacrylic acid-2-(perfluorinated nonene oxygen base) ethyl ester; temperature of reaction is 80～100 ℃; reaction times is 16～100 hours, collects fluorinated block copolymer then from reaction product.
3. method according to claim 2 is characterized in that, in the step (1):
The parts by weight of bpy are 1.72～3.83 parts;
The parts by weight of CuBr are 0.52～1.17 part;
Cinnamic parts by weight are 72.41～69.23 parts;
The parts by weight of vinyl cyanide are 23.91～22.56 parts;
The parts by weight of initiator are 1.44～3.20 parts.
4. method according to claim 2 is characterized in that: in the step (1):
The parts by weight of bpy are 0.95～2.38 part;
The parts by weight of CuBr are 0.29～0.73 part;
The parts by weight of macromole evocating agent are 10.50～33.01 parts;
The parts by weight of fluorochemical monomer methacrylic acid-2-(perfluorinated nonene oxygen base) ethyl ester are 64.19～88.21 parts.
5. method according to claim 2 is characterized in that, said initiator is selected from a kind of in alpha-brominated ethyl isobutyrate, bromine ethylbenzene, the alpha-brominated propionitrile.
6. the application of fluorinated block copolymer according to claim 1 is characterized in that, as SCCO 2The stablizer that uses in the middle polyacrylonitrile dispersion polymerization.
CNB2005100265126A 2005-06-07 2005-06-07 Fluorine-containing block copolymer and its preparation process and use thereof Expired - Fee Related CN1332992C (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100532478C (en) * 2007-09-29 2009-08-26 中国科学院广州化学研究所 Composite coating containing fluorine-containing acrylic ester block copolymer and producing method thereof
CN101899126A (en) * 2010-07-21 2010-12-01 常州大学 Miniemulsion with fluorinated block copolymers as co-stabilizers and preparation method thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5863612A (en) * 1992-03-27 1999-01-26 University North Carolina--Chapel Hill Method of making fluoropolymers
DE4441982A1 (en) * 1994-11-25 1996-05-30 Bayer Ag Oil, water and dirt-repellent substrates and fluorine-containing agents

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100532478C (en) * 2007-09-29 2009-08-26 中国科学院广州化学研究所 Composite coating containing fluorine-containing acrylic ester block copolymer and producing method thereof
CN101899126A (en) * 2010-07-21 2010-12-01 常州大学 Miniemulsion with fluorinated block copolymers as co-stabilizers and preparation method thereof

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