CN102827353A - Synthesis method of spherical organic conjugated polymer - Google Patents
Synthesis method of spherical organic conjugated polymer Download PDFInfo
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- CN102827353A CN102827353A CN2011101650802A CN201110165080A CN102827353A CN 102827353 A CN102827353 A CN 102827353A CN 2011101650802 A CN2011101650802 A CN 2011101650802A CN 201110165080 A CN201110165080 A CN 201110165080A CN 102827353 A CN102827353 A CN 102827353A
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Abstract
The invention discloses a synthesis method of a spherical granular organic conjugated polymer. The synthesis method uses 1, 3, 5-triethynylbenzene and 1, 3, 5-tribromobenzene (and the derivatives of 1, 3, 5-tribromobenzene) or 1,3,5-triiodobenzene (and the derivatives of 1, 3, 5-triiodobenzene) as substrates and comprises the steps of carrying out polymerization, filtering, washing and drying to obtain the final spherical organic conjugated polymer with a diameter about 1-3mum. According to the invention, the raw materials easily manufactured in the industry are used to prepare the organic conjugated material with a high additional value through a simple and economic method. The prepared material has a high specific surface area and an abundant pore volume and is suitable for mass production and application.
Description
Technical field
The present invention relates to a kind of compound method of form of spherical particles conjugatd polymers.
Background technology
Fossil resource in short supply day by day is a global problem with the ecotope that constantly worsens, and this makes the research of clean energy and environment protection more and more come into one's own.Nanometer micropore or mesopore material; Like zeolite molecular sieve, metal-organic framework materials, carbon nanotube, gac, organic porous polymer, etc., have bigger specific surface area and good permeability can and paid close attention to by numerous scientists; Be widely used in atmosphere storage, fractionation by adsorption, etc. the aspect.
A kind of novel porous nanometer material one conjugatd polymers occurred in these 2 years, this novel nano material has the general property of traditional porous material, and can carry out material functional modification through chemical process.
Conjugatd polymers seldom was used as porous material research in the past; These homopolymerizations or copolymeric material have pi-conjugated system; Thereby they have stable structure; Have acid-alkali-corrosive-resisting, Heat stability is good and insoluble advantage such as molten simultaneously, this type polymeric materials have bigger specific surface area, good pore volume and suitably with the reactive force of material absorption.Most of conjugatd polymerses are that unbodied form exists, and this has influenced the range of application of this base polymer greatly; And our synthetic conjugated polymers is to exist with sphere, and this base polymer has good prospects for application more in environment protection and catalytic field.
Summary of the invention
The technical problem that the present invention will solve is to provide a kind of compound method of form of spherical particles conjugatd polymers, and experimental technique is simple, can the synthetic conjugatd polymers with definite shape and particle size of mass-producing.
For solving the problems of the technologies described above, the present invention adopts following technical scheme:
A kind of compound method of spherical conjugatd polymers is to have the basic thing A 1,3 of two dimensional structure, 5-three Phenylacetylenes and basic thing B 1; 3,5-tribromo-benzene or derivatives thereof, or 1,3; 5-three Phenylacetylenes and basic thing B 1,3,5-phenyl triiodide or derivatives thereof is the reactive group thing; As catalyzer, under chemically inactive gas atmosphere, carry out polyreaction with cuprous iodide and tetrakis triphenylphosphine palladium, reaction soln is non-polar solvent C and basic solvent D.
Because basic thing A and basic thing B are two dimensional structure, they are generally two dimensional structure after polymerization, but because Br and acetylene union have certain magnetism, cause this two dimensional structure to take place to curl, and form kernel.Because after the product polymerization is two dimensional structure, and certain power that attracts each other is arranged between face and the face,, finally form ball-like structure through wrapping up layer by layer.So adopt this kind method to synthesize conjugatd polymers, polymkeric substance can continue to react the particle that makes polymkeric substance and increase.
In order to improve the rerum natura of the spherical conjugatd polymers of this type, the pore volume that the minimizing system is unnecessary can be with the verivate of tribromo-benzene or phenyl triiodide, with three Phenylacetylene polymerizations.Like-tribromophenol, toluene tribromide, etc.
Base thing A is 1,3,5-three Phenylacetylenes, basic thing B is 1,3,5-tribromo-benzene or 1,3,5-phenyl triiodide, and related derivatives, one of the structural formula of related derivatives is following, wherein R can for-H ,-CH
3,-OH or-COH in any one;
Reaction conditions is: basic thing A, basic thing B are with mol ratio 1-1.05: 1 mixes, and adds catalytic amount cuprous iodide and tetrakis triphenylphosphine palladium, under protection of inert gas, adds reaction solvent C and solvent D; Wherein solvent C can for a kind of in toluene, THF, the DMAC N,N or more than two kinds, solvent D be diethylamine or triethylamine.
Reaction mass is in inert atmosphere, and normal temperature stirs more than 1 hour down, makes the reaction mass thorough mixing, is warming up to 75-85 ℃ then rapidly, and vigorous stirring is more than 1 hour, and polymerization ofathe reactants forms spheroidal particle, and is aging more than 9 hours under 75-85 ℃ of temperature.
Beneficial effect of the present invention is:
(1) the conjugatd polymers great majority are amorphous form, and the molecule aggregation degree is uncontrollable, and the polymer beads shape is different, particle diameter differs greatly, and has limited the range of application of polymeric materials.And use present method synthetic polymer, owing between face and the face certain power that attracts each other is arranged, polymkeric substance can continued growth, forms spheroidal particle.
(2) the present invention utilizes the starting material that can make in the industry, through simple, economic method, and the porous material that preparation has high added value.This material is an organic polymer, has high specific surface area and good pore volume.Therefore, this product can be used as the carrier of sorbent material and catalyzer in industry, be with a wide range of applications.
(3) this base polymer is insoluble not fusant.In the polymeric system, be connected with acetylene bond with phenyl ring, unique conjugated system makes its physical and chemical performance good, below 300 degree, does not decompose basically.Simultaneously, can be through changing the method for basic thing B, the improvement polymer properties reduces unnecessary spatial volume.
(4) synthesis technique of this product is simple, and is not high to equipment requirements, can realize industrial-scale production.
Description of drawings
Fig. 1 is the stereoscan photograph of sample, can see containing a large amount of sphere materials in the sample.
Fig. 2 is the transmission electron microscope photo of sample.The pattern that clearly shows the conjugatd polymers that generates.
Embodiment
Below in conjunction with experimental subjects the present invention is described further, but protection scope of the present invention is not limited to this.
Following formula 1 is spherical conjugatd polymers synthetic reaction diagram for the present invention gets.
Experimental example 1
With 1,3,5-three Phenylacetylenes (300mg, 2mmol), 1,3, the 5-tribromo-benzene (630mg, 2mmol), tetrakis triphenylphosphine palladium (100mg, 0.8mmol), (30mg 0.16mmol) is placed in the exsiccant round-bottomed flask of 100ml cuprous iodide.Logical argon gas emptying gas 10min forms the anhydrous and oxygen-free environment in device.Then in device, add dry toluene (3.5ml) and anhydrous triethylamine (4ml), continue to lead to argon gas for some time, be warming up to 80 ℃ then, will be reflected under the ar gas environment vigorous stirring and react about 9h with syringe.Filter, product is used ethylene dichloride, acetone, pure water, methanol wash respectively, drying can obtain spherical organic conjugate polymerization sample 1.As illustrated in fig. 1 and 2.
Experimental example 2
With 1,3,5-three Phenylacetylenes (300mg, 2mmol), 1,3, the 5-tribromophenol (662mg, 2mmol), tetrakis triphenylphosphine palladium (100mg, 0.8mmol), (30mg 0.16mmol) is placed in the exsiccant round-bottomed flask of 100ml cuprous iodide.Logical argon gas emptying gas 10min forms the anhydrous and oxygen-free environment in device.Then in device, add dry toluene (3.5ml) and anhydrous triethylamine (4ml), continue to lead to argon gas for some time, be warming up to 80 ℃ then, will be reflected under the ar gas environment vigorous stirring and react about 9h with syringe.Filter, product is used ethylene dichloride, acetone, pure water, methanol wash respectively, drying obtains spherical organic conjugate polymerization sample 2.
The form of spherical particles organic conjugate polymeric materials that the present invention makes has good spherical morphology.The size range of bead is about 1-5 μ m, and Fig. 1 is the stereoscan photograph of sample, and Fig. 2 is the transmission electron microscope picture of sample, can clearly see the pattern of the conjugatd polymers of generation.
The present invention utilizes and is prone to the material that makes in the industry, and through simple, economic method, the organic conjugate polymeric materials of preparation high added value, this material have high-specific surface area and abundant pore volume, are applicable to scale operation and application.
Claims (4)
1. the compound method of a form of spherical particles conjugatd polymers is characterized in that: be with 1,3; 5-three Phenylacetylenes are basic thing A and with 1,3; 5-tribromo-benzene, 1,3,5-phenyl triiodide or their verivate are basic thing B; Under catalyst action, place inert gas atmosphere to carry out polyreaction and form; Reaction product obtains described form of spherical particles organic conjugate material after filtration, washing, drying.
2. compound method as claimed in claim 1 is characterized in that: basic thing A is 1,3,5-three Phenylacetylenes, basic thing B is 1,3,5-tribromo-benzene or 1,3,5-phenyl triiodide, and related derivatives, one of the structural formula of related derivatives is following, wherein R can for-H ,-CH
3,-OH or-COH in any one;
3. according to claim 1 or claim 2 compound method; It is characterized in that: reaction conditions is: basic thing A, basic thing B are with mol ratio 1-1.05: 1 mixes; Add catalyzer cuprous iodide and tetrakis triphenylphosphine palladium, under protection of inert gas, add reaction solvent C and solvent D; Wherein solvent C can for a kind of in toluene, THF, the DMAC N,N or more than two kinds, solvent D be diethylamine or triethylamine.
4. compound method as claimed in claim 3; It is characterized in that: reaction mass is in inert atmosphere, and normal temperature stirs more than 1 hour down, makes the reaction mass thorough mixing; Be warming up to 75-85 ℃ then rapidly; Vigorous stirring is more than 1 hour, and polymerization ofathe reactants forms spheroidal particle, and is aging more than 9 hours under 75-85 ℃ of temperature.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105293617A (en) * | 2014-07-18 | 2016-02-03 | 中国科学院大连化学物理研究所 | Method for treating pollutants in water by taking organic fluorine conjugated microporous polymer as adsorbent |
| CN107936261A (en) * | 2017-11-27 | 2018-04-20 | 盐城师范学院 | A kind of method of new two dimensional crystal surface catalysis two dimension organic polymer growth |
| CN109400850A (en) * | 2018-11-15 | 2019-03-01 | 上海纳米技术及应用国家工程研究中心有限公司 | The preparation method and products thereof of ultra-fine silver nano-grain and micropore organic polymer composite material |
| CN110437425A (en) * | 2019-07-30 | 2019-11-12 | 辽宁大学 | Super-hydrophobic porous organic polymer containing alkyl chain of one kind and its preparation method and application |
| CN113321786A (en) * | 2021-05-28 | 2021-08-31 | 南京理工大学 | Sulfonic conjugated microporous polymer, preparation method and application |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100240781A1 (en) * | 2007-08-15 | 2010-09-23 | Ulive Enterprises Limited | Microporous Polymers, Methods for the Preparation Thereof, and Uses Thereof |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100240781A1 (en) * | 2007-08-15 | 2010-09-23 | Ulive Enterprises Limited | Microporous Polymers, Methods for the Preparation Thereof, and Uses Thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105293617A (en) * | 2014-07-18 | 2016-02-03 | 中国科学院大连化学物理研究所 | Method for treating pollutants in water by taking organic fluorine conjugated microporous polymer as adsorbent |
| CN107936261A (en) * | 2017-11-27 | 2018-04-20 | 盐城师范学院 | A kind of method of new two dimensional crystal surface catalysis two dimension organic polymer growth |
| CN109400850A (en) * | 2018-11-15 | 2019-03-01 | 上海纳米技术及应用国家工程研究中心有限公司 | The preparation method and products thereof of ultra-fine silver nano-grain and micropore organic polymer composite material |
| CN109400850B (en) * | 2018-11-15 | 2020-12-25 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of superfine silver nano-particle and microporous organic polymer composite material and product thereof |
| CN110437425A (en) * | 2019-07-30 | 2019-11-12 | 辽宁大学 | Super-hydrophobic porous organic polymer containing alkyl chain of one kind and its preparation method and application |
| CN113321786A (en) * | 2021-05-28 | 2021-08-31 | 南京理工大学 | Sulfonic conjugated microporous polymer, preparation method and application |
| CN113321786B (en) * | 2021-05-28 | 2022-06-28 | 南京理工大学 | Sulfonic conjugated microporous polymer, preparation method and application |
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