CN110922598A - Synthetic method of benzenediol derivative type polysulfate - Google Patents

Synthetic method of benzenediol derivative type polysulfate Download PDF

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CN110922598A
CN110922598A CN201911316996.6A CN201911316996A CN110922598A CN 110922598 A CN110922598 A CN 110922598A CN 201911316996 A CN201911316996 A CN 201911316996A CN 110922598 A CN110922598 A CN 110922598A
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benzenediol derivative
polysulfate
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benzenediol
fluoride
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梁鹏强
周云斌
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Inner Mongolia Tuwei New Material Technology Co ltd
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/24—Polysulfonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
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    • C08G75/23—Polyethersulfones

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Abstract

The invention discloses a method for synthesizing benzenediol derivative type polysulfate, which comprises the following steps: (1) adding triethylamine serving as a catalyst into dichloromethane in which a benzenediol derivative compound is dissolved, stirring, and introducing sulfuryl fluoride gas to prepare a benzenedisulfonyl fluoride monomer; (2) purifying the benzene disulfonyl fluoride monomer and recovering triethylamine; (3) in the presence of an alkali catalyst, a benzenediol derivative compound and a disulfonyl fluoride monomer are polymerized at 150-200 ℃ to form benzenediol derivative type polysulfate; (4) purifying the benzenediol derivative type polythioester. The synthesis process can realize large-scale industrial production, the by-product can be recovered, the pollution is small, the process is simple and stable, and the synthesized high-crystallinity polysulfate material has better solvent resistance and higher use temperature, and has wide application prospect.

Description

Synthetic method of benzenediol derivative type polysulfate
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a method for synthesizing benzenediol derivative type polysulfate.
Background
The fluorine sulfur exchange (SuFEx) click reaction is a new generation of click chemistry reported by professor Sharpless in 2014. The system adopts cheap industrial pesticide sulfuryl fluoride (SO)2F2) Reacting with phenolic compounds to prepare substrates for SuFEx click reactions. The synthesized polysulfate material has acid resistance, alkali resistance, higher glass transition temperature,excellent mechanical property.
The high-valence main group fluoride has high chemical stability, but the activation of the high-valence main group fluoride under specific conditions can realize extremely efficient chemical bond transformation and linkage, and the combination of the special stability and the reactivity determines that the compound has unique potential application in organic synthetic chemistry, material chemistry, chemical biology and medicinal chemistry. The success of the hexavalent sulfur fluorine exchange reaction (SuFEx) is precisely the use of this particular reactivity of the hexavalent sulfur fluorine bond. Since 2014, the teaching of sharp (angel. chem. int.ed.2014,9430) firstly proposed and successfully realized the exchange reaction of hexavalent sulfur and fluorine, the reaction has attracted extensive attention in the aspects of organic synthesis chemistry, material chemistry, pharmaceutical chemistry, chemical biology, particularly protein molecule selective marking and modification, etc., and has shown good application prospect, which is called as the new generation click chemistry, and becomes a new hot point of the current fluorine chemistry research.
However, because of the limitations of the traditional synthesis method and process of the polysulfate material, industrial mass production cannot be realized, and the application thereof is seriously affected, so how to provide a feasible scheme for the industrialization of the polysulfate material is a problem to be solved in the field.
Disclosure of Invention
The invention aims to: the synthetic method of the benzenediol derivative type polysulfate can realize large-scale industrial production, by-products can be recovered, pollution is small, the process is simple and stable, and the synthesized polysulfate type material with high crystallinity has better solvent resistance, higher use temperature and wide application prospect.
The technical scheme adopted by the invention is as follows:
in order to achieve the above object, the present invention provides a method for synthesizing benzenediol derivative type polysulfate, comprising the steps of:
(1) adding triethylamine serving as a catalyst into dichloromethane in which a benzenediol derivative compound is dissolved, stirring, and introducing sulfuryl fluoride gas to prepare a benzenedisulfonyl fluoride monomer;
(2) purifying the benzene disulfonyl fluoride monomer and recovering triethylamine;
(3) in the presence of an alkali catalyst, a benzenediol derivative compound and a disulfonyl fluoride monomer are polymerized at 150-200 ℃ to form benzenediol derivative type polysulfate;
(4) purifying the benzenediol derivative type polythioester.
Preferably, the diphenol derivative compound comprises the following structural formula:
Figure BDA0002326093780000021
wherein R is-OSO2F；R1，R2，R3，R4Is any one of-H, alkyl containing 1-6 carbon atoms, halogen substituent, sulfonyl fluoride, nitryl and carboxyl;
r1, R2 and the carbon atoms therebetween may together form a benzene ring;
R1，R2，R3，R4may be mono-substituted or poly-substituted.
Preferably, the benzene disulfonyl fluoride monomer comprises the following structural formula:
Figure BDA0002326093780000022
wherein R is-OSO2F；R1，R2，R3，R4Is any one of-H, alkyl containing 1-6 carbon atoms, halogen substituent, sulfonyl fluoride, nitryl and carboxyl;
r1, R2 and the carbon atoms therebetween may together form a benzene ring;
R1，R2，R3，R4may be mono-substituted or polysubstituted。
Preferably, in the step (3), the molar ratio of the diphenol derivative compound, the benzenedisulfonyl fluoride monomer and the catalyst is 1: (1-1.02): 2.2, most preferably in a molar ratio of 1: 1.02: 2.2.
preferably, in the step (2), the purification of the disulfonyl fluoride monomer is performed by using methanol or ethanol, the purity of the high performance liquid phase purity test is 85% -99.5%, the yield is 60% -90%, and the product is kilogram grade; the triethylamine is recovered by adding an alkali solution into the recovered by-product and distilling to recover the triethylamine; the alkali can be lithium carbonate, cesium carbonate, DBU or potassium hydroxide, wherein lithium carbonate is most preferred.
Preferably, in the step (3), the catalyst is selected from any one or a mixture of sodium hydroxide, potassium bifluoride, sodium carbonate, potassium carbonate, lithium carbonate, calcium oxide, magnesium oxide, triethylamine, DBU, potassium fluoride, lithium carbonate, calcium stearate, and magnesium stearate, wherein the combination of sodium hydroxide and potassium bifluoride is most preferable.
Preferably, the polymerization reaction in step (3) is carried out in a solvent selected from any one of NMP, DMF, DMSO, DMAC, sulfolane, nitrobenzene, and most preferably nitrobenzene, or the polymerization reaction is solvent-free melt polymerization.
Preferably, an antioxidant is added in a mass fraction of 5% in the polymerization reaction of step (3).
Preferably, the antioxidant is selected from any one or a mixture of sodium sulfite, sodium hydrosulfite, iron powder, sodium thiosulfate and manganese dioxide, wherein iron powder is most preferred.
Preferably, the step (4) is specifically: dissolving and settling benzenediol derivative type polysulfate with NMP solution, removing inorganic salt with purified water at high pressure and high temperature, and removing residual monomer and small molecules in the polymer with methanol at high temperature and high pressure.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. the invention introduces p-phenylene diphenol monomer into the polysulfate material to prepare the polysulfate material with high crystallinity, and the crystalline polysulfate has greatly improved use temperature (Tm is 233 ℃) for the material, thereby having wide application prospect in the fields of aviation, communication, electronics and microelectronic industry.
2. Compared with double-bond type crystalline polysulfate, the p-phenylene diphenol type crystalline polysulfate synthesized by the invention has the advantages of easily available and cheap raw materials, low production cost, mild reaction conditions, high yield, narrow molecular weight distribution, easy preparation of high molecular weight polymer, simple and stable synthesis process and realization of kilogram-level continuous production.
3. In the synthesis process, no water is involved in the benzene disulfonyl fluoride post-treatment process, the sewage treatment pressure is reduced, the by-products are recovered and reused, and the production cost is reduced.
4. Compared with the traditional polyester synthesis method, the synthesis process is economical, the byproduct is fluoride inorganic salt, the fluoride inorganic salt can be sold as an industrial product, the environmental pollution is low, and the industrial production is facilitated.
Drawings
FIG. 1 is a secondary temperature rise curve-DSC of hydroquinone-type polysulfate;
FIG. 2 is a resorcinol type polysulfate XRD;
FIG. 3 is a hydroquinone type polysulfate XRD;
FIG. 4 is a bisphenol S hydroquinone copoly sulfate XRD;
FIG. 5 is a bisphenol A hydroquinone copoly sulfate XRD;
FIG. 6 is a carbon spectrum of hydroquinone sulfonyl monomer;
FIG. 7 is a hydroquinone sulfuryl fluoride monomer hydrogen spectrum.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A method for synthesizing benzenediol derivative type polysulfate comprises the following steps:
preparation of mono, 1, 4-diphenyl sulfonyl fluoride monomer
(1) 5kg of benzenediol monomer with the purity of more than 99.5 percent is firstly put into a 50L high-pressure kettle; adding 30L of dichloromethane solvent, stirring in a high-pressure kettle in a closed manner at an industrial level, and stirring at normal temperature; 11027.88g of triethylamine is added, the temperature is 25 ℃, after stirring for 30min, 10898.4g of sulfuryl fluoride gas is added in batches under high pressure, and the reaction time is 16 h.
And (2) carrying out reduced pressure rotary evaporation on the mixture obtained in the step (1) in a water bath at 35 ℃, removing the solvent DCM, recovering, adding 24L of methanol solution into the rest system, heating at 80 ℃, boiling, refluxing, slowly crystallizing after the system is clear, and filtering out a solid to obtain a target product, wherein 9920.8g of white needles are obtained, and the purity of high performance liquid chromatography is 99.5%.
And (3) distilling the methanol filtrate obtained in the step (2) in 70 ℃ water bath under reduced pressure to obtain a yellow viscous liquid finally remained in the system, pouring the viscous liquid into a glass three-neck flask, erecting a distillation device, slowly adding lithium carbonate powder into the system, magnetically stirring, heating to 80 ℃ after the reaction is finished, recovering triethylamine, wherein the recovered triethylamine is a transparent liquid with the mass of 955g, and recovering the remained lithium fluoride aqueous solution.
Synthesis of di-hydroquinone type poly-sulfuric ester
(1) 1000g of hydroquinone is weighed, 2530.78g of the 1, 4-diphenylsulfonyl fluoride monomer prepared previously, 799.216g of sodium hydroxide, 35g of potassium fluorocyanate, 16.13L of nitrobenzene solution and 50g of iron powder are added into a polymerization kettle at one time and stirred, and the temperature is raised to 170-220 ℃ from room temperature. The temperature rise time is 2h, 4h and 2h, and after the reaction is finished, the materials are discharged under pressure by nitrogen and are settled in an ethanol solution.
(2) Adding the obtained polymer into a 10L high-pressure kettle, adding 5L of purified water, boiling at 120 ℃ for 5 hours, repeating for 1 time, drying, repeatedly boiling with 6L of methanol solution at 100 ℃ for one time, and drying to obtain the hydroquinone type polysulfate.
Example 2
Preparation of mono, 1, 4-diphenyl sulfonyl fluoride monomer
The preparation method is the same as that of example 1
Synthesis of di-and bisphenol A and hydroquinone copolymerized polysulfate
(1) 1000g of p-bisphenol A monomer, 1220.6g of the 1, 4-diphenylsulfonyl fluoride monomer prepared above, 385.44g of sodium hydroxide, 15g of potassium fluorocyanate, 16.13L of nitrobenzene solution and 50g of iron powder are weighed out and added into a polymerization kettle at a time, and the temperature is raised to 170-220 ℃ from room temperature. The temperature rise time is 2h, 4h and 2h, and after the reaction is finished, the materials are discharged under pressure by nitrogen and are settled in an ethanol solution.
(2) Adding the obtained polymer into a 10L high-pressure kettle, adding 5L of purified water, boiling at 120 ℃ for 5 hours, repeating for 1 time, drying, then repeatedly boiling with 6L of methanol solution at 100 ℃ for one time, and drying to obtain the bisphenol A hydroquinone copolymerization type polysulfate.
Example 3
Preparation of mono, 1, 3-diphenyl sulfonyl fluoride monomer
Synthesis of di-resorcin and bisphenol A copolymer type polysulfate
(1) 1000g of p-bisphenol A monomer, 1220.6g of 1, 3-diphenylsulfonyl fluoride monomer obtained in example 1, 385.44g of sodium hydroxide, 15g of potassium fluorocyanate, 16.13L of nitrobenzene solution, and 50g of iron powder were weighed out and added to a polymerization vessel in one portion, and the temperature was raised from room temperature to 170 ℃ to 220 ℃. The temperature rise time is 2h, 4h and 2h, and after the reaction is finished, the materials are discharged under pressure by nitrogen and are settled in an ethanol solution.
(2) And adding the obtained polymer into a 10L high-pressure kettle, adding 5L of purified water, boiling for 5 hours at 120 ℃, repeating for 1 time, drying, repeatedly boiling once at 100 ℃ with 6L of methanol solution, and drying to obtain the resorcinol bisphenol A copolymerized polysulfate.
Test examples
The solvent resistance test of the product of the invention, heating and dissolving the polymer of the invention in 1mg/ml solvent, mainly selects the solvent with high polarity and strong solubility to dissolve, and the solvents have good solubility to the PC and PSU sold in the market under heating condition.
TABLE 1 results of solvent resistance test
Figure BDA0002326093780000051
Figure BDA0002326093780000061
As can be seen from Table 1, the polymer material of the present invention shows insolubility in most of the dissolution, has excellent solvent resistance, and has potential application market as a solvent resistant material.
From FIG. 1, it can be seen that the melting point of the polymer is 233 deg.C, and the crystallization temperature is 197.9 deg.C in the temperature drop curve, and it can be seen that the polymer of the present invention has a great increase in the use temperature.
From the XRD curves shown in fig. 2 to 5, it can be seen that resorcinol and hydroquinone are crystalline polymers, and bisphenol S and hydroquinone are copolymer polysulfates, and bisphenol a and hydroquinone are copolymer polysulfates, and amorphous polymers.
Two sets of peaks, combined with the carbon spectrum of hydroquinone monomer (figure 6), correspond to two different environments of carbon in the compound, respectively, and the hydrogen spectrum (figure 7) corresponds to one environment of hydrogen.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; these modifications and substitutions do not cause the essence of the corresponding technical solution to depart from the scope of the technical solution of the embodiments of the present invention, and are intended to be covered by the claims and the specification of the present invention.

Claims (10)

1. A method for synthesizing benzenediol derivative type polysulfate is characterized by comprising the following steps:
(1) adding triethylamine serving as a catalyst into dichloromethane in which a benzenediol derivative compound is dissolved, stirring, and introducing sulfuryl fluoride gas to prepare a benzenedisulfonyl fluoride monomer;
(2) purifying the benzene disulfonyl fluoride monomer and recovering triethylamine;
(3) in the presence of a catalyst, a benzenediol derivative compound and a benzenedisulfonyl fluoride monomer are polymerized at 150-220 ℃ to form benzenediol derivative type polysulfate;
(4) purifying the benzenediol derivative type polythioester.
2. The method of claim 1, wherein the benzenediol derivative type polythioester comprises the following structural formula:
Figure FDA0002326093770000011
wherein R is-OSO2F；R1，R2，R3，R4Is any one of-H, alkyl containing 1-6 carbon atoms, halogen substituent, sulfonyl fluoride, nitryl and carboxyl;
r1, R2 and the carbon atoms therebetween may together form a benzene ring;
R1，R2，R3，R4may be mono-substituted or poly-substituted.
3. The method of claim 1, wherein the benzene disulfonyl fluoride monomer has the following structural formula:
Figure FDA0002326093770000012
wherein R is-OSO2F；R1，R2，R3，R4is-H, alkyl having 1 to 6 carbon atoms, halogenAny one of an element substituent, sulfonyl fluoride, nitro and carboxyl;
r1, R2 and the carbon atoms therebetween may together form a benzene ring;
R1，R2，R3，R4may be mono-substituted or poly-substituted.
4. The method for synthesizing benzenediol derivative type polythioate as claimed in any one of claims 1 to 3, wherein in step (3), the molar ratio of benzenediol derivative compound, benzenedisulfonyl fluoride monomer and catalyst is 1: (1-1.02): 2.2.
5. the method for synthesizing benzenediol derivative type polysulfate as claimed in claims 1 to 3, wherein in the step (2), the purification of the disulfonyl fluoride monomer is performed by using methanol, the recovery of triethylamine is performed by adding an alkali solution into the recovered by-product, and the triethylamine is recovered by distillation; the alkali can be lithium carbonate, cesium carbonate, DBU or potassium hydroxide.
6. The method for synthesizing benzenediol derivative type polysulfate as claimed in any one of claims 1 to 3, wherein in step (3), the catalyst is selected from any one or a mixture of sodium hydroxide, potassium bifluoride, sodium carbonate, potassium carbonate, lithium carbonate, calcium oxide, magnesium oxide, triethylamine, DBU, potassium fluoride, lithium carbonate, calcium stearate, and magnesium stearate.
7. The method for synthesizing benzenediol derivative-type polythioate as claimed in any one of claims 1 to 3, wherein the polymerization reaction in step (3) is performed in a solvent selected from one of NMP, DMF, DMSO, DMAC, sulfolane and nitrobenzene, or the polymerization reaction is solvent-free melt polymerization.
8. The method for synthesizing benzenediol derivative-type polythioate as claimed in any one of claims 1 to 3, wherein an antioxidant is added in an amount of 5% by mass in the polymerization reaction of step (3).
9. The method for synthesizing benzenediol derivative type polythioate as claimed in any one of claims 1 to 3, wherein the antioxidant is selected from any one or a mixture of sodium sulfite, sodium hydrosulfite, iron powder, sodium thiosulfate and manganese dioxide.
10. The method for synthesizing benzenediol derivative type polythioate as claimed in any one of claims 1 to 3, wherein the step (4) specifically comprises: dissolving and settling benzenediol derivative type polysulfate with an organic solvent, removing inorganic salts with purified water at high pressure and high temperature, and removing residual monomers and small molecules in the polymer with methanol at high temperature and high pressure.
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Cited By (5)

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CN112898571A (en) * 2021-01-29 2021-06-04 苏州大学 Porous cross-linked material and preparation method and application thereof
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