CN111040165A - Polysulfonate polymer and polymerization method thereof - Google Patents
Polysulfonate polymer and polymerization method thereof Download PDFInfo
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Abstract
The invention discloses a polysulfonate polymer and a polymerization method thereof, wherein p-hydroxybenzene sulfonyl fluoride is used as a raw material, under the conditions of inert gas protection and catalyst existence, the p-hydroxybenzene sulfonyl fluoride is subjected to self polymerization or reacts with bisphenol or diamine protected by trialkyl silicon base at the temperature of 30-120 ℃ for 3-36 h, a reaction mixture is poured into water or butanol and other solvents, and the precipitated polymer is the product polysulfonate polymer. The polysulfonate polymer has excellent solvent resistance, mechanical property, dielectric property and biocompatibility, and has low biological toxicity after decomposition, so the polysulfonate polymer has wide application prospect in the fields of medicines, food packaging and the like. In addition, the invention introduces a new polymerization mode in the synthesis process, the reaction flow is simple, the yield is high, and the obtained polymer has higher molecular weight, thereby being beneficial to widening the application scene of the polymer.
Description
Technical Field
The invention belongs to the technical field of high molecular materials, and particularly relates to a polysulfonate polymer and a polymerization method thereof.
Background
Polyester is one of the most important chemical synthetic materials, and is widely applied to the fields of fibers, packaging, engineering plastics, medical materials and the like. The global polyester industry has been rapidly developing over the last 20 years, driven by technological advances and market demands. After a great deal of research and improvement on the synthesis process of polyester, an optimized process route with simple process flow, high energy-saving efficiency, less pollution, high product recovery efficiency and the like can be obtained.
The major varieties of polyesters currently include high molecular weight compounds such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT) and polyarylates, as well as certain copolyester families. Polyester resin has been widely used in the field of packaging materials, molded articles, and films, and moreover, it is one of environment-friendly plastics having no endocrine disruptor (dissiptor). The demand for environmentally friendly transparent and heat-resistant polyester resins has increased more. The polysulfonate is an excellent functional thermoplastic material, integrates the mechanical properties of polycarbonate and the advantages of heat resistance and chemical resistance of polysulfone, has high strength, high insulation, high heat resistance, good corrosion resistance and weather resistance, and has the advantages of transparency, no toxicity, strong self-extinguishing capability, high dimensional stability and wide plasticizing temperature range. The method is applied to a series of advanced technical fields of electrical industry, mechanical industry, instrument industry and the like.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a polysulfonate polymer and a polymerization method thereof.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
firstly, polysulfonate polymer and synthesis thereof:
the structural formula of the polysulfonate polymer is shown as the following A or B:
in the formula R1is-Me, -Et, -Ph, -iPr or-H;
R2is-Me, -Et, -Ph, -iPr or-H;
R3is-Me, -Et, -Ph, -iPr or-H;
R4is-Me, -Et, -Ph, -iPr or-H;
R5is-Me, -Et, -Ph, -iPr or-H;
R6is-Me, -Et, -Ph, -iPr or-H;
x is-C, -Si, -O;
n＝10～1000。
the synthesis method of the polysulfonate polymer comprises the following two process steps:
(1) synthesizing a raw material benzenesulfonyl fluoride monomer: dissolving sodium benzenesulfonate in thionyl chloride, adding 0.1% of DMF as a catalyst, reacting for 4-20 h (preferably 12h) at 40-80 ℃ (preferably 50 ℃), quenching after the reaction is finished, extracting with dichloromethane, continuously reacting with KF or KHF2 for 2-10 h, and washing with water to obtain the product benzenesulfonyl fluoride. The reaction is represented by the following chemical formula:
in the formula R1is-Me, -Et, -Ph, -iPr or-H;
R2is-Me, -Et, -Ph, -iPr or-H;
R3is-Me, -Et, -Ph, -iPr or-H;
R4is-Me, -Et, -Ph, -iPr or-H;
R5is-Me, -Et, -Ph, -iPr or-H;
R6is-Me, -Et, -Ph, -iPr or-H;
x is-C, -Si, -O.
(2) The synthesis method of the polysulfonate polymer comprises the following steps:
the method comprises the following steps of taking benzenesulfonyl fluoride as a raw material, carrying out self-polymerization or reacting the benzenesulfonyl fluoride with trialkyl silicon-based protected bisphenol or diamine at the temperature of 30-120 ℃ for 3-36 h under the protection of inert gas and the presence of a catalyst, pouring a reaction mixture into water or a solvent such as butanol, and obtaining a precipitated polymer, namely the product polysulfonate polymer. The above reaction formula is represented as follows:
in the formula R1is-Me, -Et, -Ph, -iPr or-H;
R2is-Me, -Et, -Ph, -iPr or-H;
R3is-Me, -Et, -Ph, -iPr or-H;
R4is-Me, -Et, -Ph, -iPr or-H;
R5is-Me, -Et, -Ph, -iPr or-H;
R6is-Me, -Et, -Ph, -iPr or-H;
r' is-TMS, -TES, -H or-TBS;
x is-C, -Si, -O;
n＝10～1000。
the catalyst is one of the following raw materials: 1, 8-diazabicyclo (5, 4, 0) -undec-7-ene (DBU), 1, 8-diazabicyclo (5, 4, 0) -undec-7-ene phenol salt, 1, 8-diazabicyclo (5, 4, 0) -undec-7-ene-ethylhexanoate, 1, 4-diazabicyclo (2, 2, 2) octane, 4-dimethylaminopyridine, dimethylcyclohexylamine, triethylenediamine-2-ethylhexanoate; the ratio of the catalyst to the benzenesulfonyl fluoride is 1: 2-1: 100 (preferably 1: 10).
Organic solvents which may be used during the polymerization are dichloromethane, dichloroethane, chloroform, ethyl acetate, acetonitrile, toluene, dioxane, N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), N, N-Dimethylformamide (DMF), Dimethylacetamide (DMAC).
The method for synthesizing the polysulfonate polymer can adopt two polymerization methods of solvent polymerization and solvent-free polymerization, if solvent polymerization is carried out, N-methyl pyrrolidone is selected as an organic solvent, if solvent polymerization is carried out, benzenesulfonyl fluoride is dissolved, and then heating is carried out for polymerization.
The polymerization reaction time can be regulated within 3-36 h according to different raw material requirements, and the polymerization degree of the polymer is regulated by adding water or butanol to terminate the reaction.
The synthetic product of the invention is analyzed by nuclear magnetism, DSC and gel chromatography, which shows that the target product-polysulfonate polymer is successfully synthesized. The specific data are shown in the attached drawings of the specification.
Compared with the prior art, the invention has the following characteristics and beneficial effects:
properties of polysulfonate-based Polymer:
1. physical property index
The polysulfonate polymer is a colorless or white transparent or semitransparent thermoplastic material.
2. Index of chemical properties
The polysulfonate polymer has good solvent resistance and biocompatibility, and has low biological toxicity after decomposition, so the polysulfonate polymer has wide application prospect in the fields of medicines, food packaging and the like. In addition, the invention introduces a new polymerization mode in the synthesis process, the reaction flow is simple, the yield is high, and the obtained polymer has higher molecular weight, thereby being beneficial to widening the application scene of the polymer.
Drawings
FIG. 1 HPLC chromatogram of p-hydroxy-phenyl sulfonate monomer;
FIG. 2 gas chromatography of p-hydroxy-phenyl sulfonate monomer;
FIG. 3 polysulfonate-based polymers1H-NMR spectrum;
FIG. 4 polysulfonate-based polymers13A C-NMR spectrum;
FIG. 5 shows a gel-chromatographic analysis of,
a weight average molecular weight (Mw) of 1.146e +4,
the number average molecular weight (Mn) is 7.011e +4,
polydispersity index (PDI [ Mw/Mn ]) 1.635,
polymerization degree: 350-360 parts;
FIG. 6 DSC analysis of polysulfonate, the glass transition temperature of the resulting p-hydroxy-phenyl sulfonate polymer was 168 ℃ according to DSC spectrum.
Detailed Description
The invention will now be further illustrated, but not by way of technical limitation, with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
Example 1
Synthesis of self-polymerized polymer by using p-hydroxybenzene sulfonyl fluoride as raw material
(1) Synthesis of p-hydroxybenzene sulfonyl fluoride: dissolving 10g of p-hydroxybenzene sodium sulfonate in 20ml of thionyl chloride, adding 0.1g of DMF, heating to 50 ℃ for reaction for 12h, pouring into crushed ice for quenching, extracting with dichloromethane, then spin-drying to obtain a product, reacting with potassium fluoride/potassium bifluoride for 8h by using water as a solvent, and layering to obtain the product p-hydroxybenzene sulfonyl fluoride.
Nuclear magnetic analysis data of the synthesized product:1H-NMR(400MHz,DMSO)δ7.32(d,2H)-7.90(d,2H).13C-NMR(400MHz,DMSO)δ121.26,124,61,130.11,131.11,131.84,132.73,153.24,154.06
the structural formula of the synthesized product is as follows:
(2) synthesis of a self-polymerizable Polymer from p-hydroxybenzene sulfonyl fluoride starting Material 10g of p-hydroxybenzene sulfonyl fluoride are dissolved in 20ml of N-methylpyrrolidone, 10% by mole of DBU (1, 8-diazabicyclo (5, 4, 0) -undec-7-ene) as a catalyst are added, the reaction is stirred at 50 ℃ for 12 hours, the mixture is then poured into water or butanol to terminate the reaction, the precipitated polymer is isolated, extracted with ethanol and dried to give 8g of a white powdery polymer in a yield of 80%. The polymer product has the following performance indexes:
weight average molecular weight (Mw) 114642
Number average molecular weight (Mn) 70110
Polydispersity index (PDI [ Mw/Mn ]) of 1.635
Polymerization degree: 350-360
Solvent resistance: chloroform, ethyl acetate, acetonitrile, toluene, dioxane, etc., and N-methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO), N, N-dimethyl formamide (DMF), dimethyl acetamide (DMAC), etc., by heating to 100 deg.C or above, it can be dissolved in small amount.
In the above polymerization, when 1, 8-diazabicyclo (5, 4, 0) -undec-7-ene (DBU), 1, 8-diazabicyclo (5, 4, 0) -undec-7-ene phenol salt, 1, 8-diazabicyclo (5, 4, 0) -undec-7-ene-ethylhexanoate, 1, 4-diazabicyclo (2, 2, 2) octane, 4-dimethylaminopyridine, dimethylcyclohexylamine, triethylenediamine-2-ethylhexanoate are used as polymerization catalysts, a self-polymerizing polymer using p-hydroxybenzene sulfonyl fluoride of this type as a raw material can be obtained.
Example 2
Heterogeneous synthesis of self-polymerized polymer by using p-hydroxybenzene sulfonyl fluoride as raw material
10g of p-hydroxybenzenesulfonyl fluoride are taken and 10% by molar weight of sodium carbonate (NaCO) as catalyst are added3) Stirring and reacting for 2h at 50 ℃, heating to 150 ℃ and continuing to react for 2h, then pouring the viscous polymer into water or butanol to terminate the reaction, separating the precipitated polymer, extracting by ethanol, and drying to obtain 9g of white powdery polymer, wherein the yield is 90%. The IR spectrum of the polymer is shown in FIG. 2. The polymer product has the following performance indexes:
weight average molecular weight (Mw) 29736
Number average molecular weight (Mn) 20676
Polydispersity index (PDI [ Mw/Mn ]) of 1.438
Polymerization degree: 105 to 110
Solvent resistance: chloroform, ethyl acetate, acetonitrile, toluene, dioxane, etc., and N-methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO), N, N-dimethyl formamide (DMF), dimethyl acetamide (DMAC), etc., by heating to 100 deg.C or above, it can be dissolved in small amount.
In the above polymerization, when 1, 8-diazabicyclo (5, 4, 0) -undec-7-ene (DBU), 1, 8-diazabicyclo (5, 4, 0) -undec-7-ene phenol salt, 1, 8-diazabicyclo (5, 4, 0) -undec-7-ene-ethylhexanoate, 1, 4-diazabicyclo (2, 2, 2) octane, 4-dimethylaminopyridine, dimethylcyclohexylamine, triethylenediamine-2-ethylhexanoate are used as polymerization catalysts, a self-polymerizing polymer using p-hydroxybenzene sulfonyl fluoride of this type as a raw material can be obtained.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (8)
1. A polysulfonate-based polymer characterized by having a structural formula shown as A or B below:
in the formula R1is-Me, -Et, -Ph, -iPr or-H;
R2is-Me, -Et, -Ph, -iPr or-H;
R3is-Me, -Et, -Ph, -iPr or-H;
R4is-Me, -Et, -Ph, -iPr or-H;
R5is-Me, -Et, -Ph, -iPr or-H;
R6is-Me, -Et, -Ph, -iPr or-H;
x is-C, -Si, -O;
n＝10～1000。
2. the polymerization method of polysulfonate polymers as claimed in claim 1, wherein benzenesulfonyl fluoride is self-polymerized or reacted with trialkylsilyl protected bisphenol or bisamine at 30-120 ℃ for 3-36 h under the protection of inert gas and in the presence of catalyst, the reaction mixture is poured into water or butanol and the precipitated polymer is the product polysulfonate polymer.
3. The method for polymerizing a polysulfonate-based polymer of claim 2 wherein the benzenesulfonyl fluoride has the formula A or B as follows:
in the formula R1is-Me, -Et, -Ph, -iPr or-H;
R2is-Me, -Et, -Ph, -iPr or-H;
R3is-Me, -Et, -Ph, -iPr or-H;
R4is-Me, -Et, -Ph, -iPr or-H;
R5is-Me, -Et, -Ph, -iPr or-H;
R6is-Me, -Et, -Ph, -iPr or-H;
x is-C, -Si, -O.
4. The method of claim 2, wherein the trialkyl silyl protected bisphenol has the following structural formula:
wherein R' is-TMS, -TES, -H or-TBS.
5. The polymerization method of polysulfonate-based polymers of claim 2 or 3 wherein benzenesulfonyl fluoride is synthesized by: dissolving sodium benzenesulfonate in thionyl chloride, adding 0.1% of DMF as a catalyst, reacting for 4-20 h at 40-80 ℃, quenching after the reaction is finished, extracting with dichloromethane, continuously reacting with KF or KHF2 for 2-10 h, and washing with water to obtain the product benzenesulfonyl fluoride.
6. The method of claim 2, wherein the catalyst is one of 1, 8-diazabicyclo (5, 4, 0) -undec-7-ene (DBU), 1, 8-diazabicyclo (5, 4, 0) -undec-7-ene phenoxide, 1, 8-diazabicyclo (5, 4, 0) -undec-7-ene-ethylhexanoate, 1, 4-diazabicyclo (2, 2, 2) octane, 4-dimethylaminopyridine, dimethylcyclohexylamine, triethylenediamine-2-ethylhexanoate; the ratio of the catalyst to the benzenesulfonyl fluoride is 1: 2-1: 100.
7. the method for polymerizing a polysulfonate-based polymer of claim 2, wherein the reaction is carried out in an organic solvent.
8. The method for polymerizing a polysulfonate-based polymer of claim 7 wherein the organic solvent is dichloromethane, dichloroethane, chloroform, ethyl acetate, acetonitrile, toluene, dioxane, N-methylpyrrolidone, dimethylsulfoxide, N, N-dimethylformamide, dimethylacetamide.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111822053A (en) * | 2020-07-22 | 2020-10-27 | 中山大学 | Chiral polysulfonate diamine-metal catalyst and synthesis and application thereof |
| CN117225017A (en) * | 2023-11-14 | 2023-12-15 | 内蒙古图微新材料科技有限公司 | Preparation device and preparation method of polysulfonate flat ultrafiltration membrane |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111822053A (en) * | 2020-07-22 | 2020-10-27 | 中山大学 | Chiral polysulfonate diamine-metal catalyst and synthesis and application thereof |
| CN117225017A (en) * | 2023-11-14 | 2023-12-15 | 内蒙古图微新材料科技有限公司 | Preparation device and preparation method of polysulfonate flat ultrafiltration membrane |
| CN117225017B (en) * | 2023-11-14 | 2024-01-30 | 内蒙古图微新材料科技有限公司 | Preparation device and preparation method of polysulfonate flat ultrafiltration membrane |
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