阅读说明：本技术 硫酸（胺）酯类连接子聚合物的聚合方法 (Polymerization method of sulfuric acid (amine) ester linker polymer ) 是由 蒋先兴 周云斌 于 2019-04-16 设计创作，主要内容包括：本发明涉及一种硫酸(胺)酯类连接子聚合物的合成方法,包括：将含羟基单体或含氨基单体与硫酰氟单体在碱性条件下通过一锅法发生缩聚反应。本发明与传统聚酯合成方法相比,经济节约；反应条件温和易控,反应流程简单,易于操作；后处理工艺简单,环境污染小,有利于工业化生产。另外,本发明合成的双酚型聚硫酸酯类化合物具有优良的机械性能、介电性能、耐受性能及耐磨性能。(The invention relates to a synthetic method of a sulfuric acid (amine) ester linker polymer, which comprises the following steps: carrying out polycondensation reaction on a hydroxyl-containing monomer or an amino-containing monomer and a sulfuryl fluoride monomer by a one-pot method under an alkaline condition. Compared with the traditional polyester synthesis method, the method is economical and economical; the reaction condition is mild and easy to control, the reaction flow is simple, and the operation is easy; the post-treatment process is simple, the environmental pollution is small, and the method is favorable for industrial production. In addition, the bisphenol type polysulfate compound synthesized by the method has excellent mechanical property, dielectric property, tolerance property and wear resistance.)

1. A method for synthesizing a sulfuric acid (amine) ester linker polymer comprises the following steps:

Carrying out polycondensation reaction on a hydroxyl-containing monomer or an amino-containing monomer and a sulfuryl fluoride monomer by a one-pot method under an alkaline condition, wherein,

The structural formula of the hydroxyl-containing monomer is HO-X (-OH) a, wherein X is a heterocyclic-containing aromatic compound, a non-heterocyclic-containing aromatic compound, aliphatic hydrocarbon, amino acid or amino acid derivative, a is an integer from 1 to 3,

The structural formula of the amino-containing monomer is H2N-Z (-NH2) b, wherein Z is a heterocyclic-containing aromatic compound, a non-heterocyclic-containing aromatic compound, aliphatic hydrocarbon, amino acid or an amino acid derivative, b is an integer from 1 to 3,

The sulfuryl fluoride monomer has a structural formula of FO2S-Y-SO2F, wherein Y is an aromatic compound, aliphatic hydrocarbon, amino acid or amino acid derivative.

2. The method of claim 1, wherein in the sulfuryl fluoride monomer of formula FO2S-Y-SO2F, Y is an aromatic or hydrocarbon compound comprising at least one functional group selected from the group consisting of sulfonyl, carbonyl, amide, ether, and heteroaryl.

3. The method of claim 1, wherein the hydroxyl-containing monomer is a bisphenol monomer having the formula of the sulfuryl fluoride monomer, wherein R and R 'are the same or different, and R' are-S-, -O-, -CH2, -C (CH3)2, -C (CF3)2, -C (O) -, -S (O)2-, -C (O) NH-or-C (O) O-.

4. the method of synthesis according to claim 1, wherein the basic conditions are achieved by addition of an inorganic base.

5. The method of claim 4, wherein the molar ratio of the inorganic base to the sulfuryl fluoride monomer is from 0.5:1 to 4: 1.

6. the synthesis method of claim 4, wherein the inorganic base is at least one selected from the group consisting of potassium phosphate, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate and cesium carbonate.

7. The method of synthesis according to claim 1, wherein the polycondensation reaction occurs in a solvent or without a solvent.

8. The method of claim 7, wherein the solvent is at least one selected from the group consisting of sulfolane, N Dimethylformamide (DMF), N Dimethylacetamide (DEF), Dimethylsulfoxide (DMSO), N-methylpyrrolidone (NMP), chlorobenzene, xylene, trimethylbenzene, tetrahydrofuran, N-hexane, and cyclopentane, and wherein the solvent comprises at least one water-carrying agent selected from the group consisting of chlorobenzene, xylene, trimethylbenzene, and N-hexane.

9. The method of synthesis according to claim 7, wherein the polycondensation reaction is carried out in a molten state of the hydroxyl group-containing monomer or the amino group-containing monomer and the sulfuryl fluoride monomer when the polycondensation reaction is carried out in the absence of a solvent.

10. The method of synthesis according to claim 1, wherein the method of synthesis comprises a capping reaction or a terminal modification reaction after completion of the polycondensation reaction.

11. The method of claim 10, wherein the end-capping reagent in the end-capping reaction is at least one selected from the group consisting of methyl chloride, phenol derivatives, and fluorobenzophenone monofunctional compounds.

12. A (amine) sulfate-based linker polymer made by the synthesis method of any of claims 1-11.

Technical Field

The invention belongs to the technical field of high polymer materials, and particularly relates to a sulfuric acid (amine) ester polymer which is prepared by carrying out polycondensation reaction on phenol or alcohol or amino and sulfuryl fluoride or sulfuryl fluoride under the action of alkali.

Background

With the continuous progress of science and technology, the polyester industry has been rapidly developed in recent years as one of important chemical synthetic materials. At present, polyester materials are widely applied to the fields of fiber manufacturing, packaging, engineering plastics, electronic and electric products, medical materials, buildings, automobiles and the like. Compared with the prior art, the polyester material has the advantages of simpler and easier synthesis, high utilization rate of raw material monomers, lower cost and the like. Therefore, polyester-based materials have been widely used in industrial production and daily life of people.

however, even though polyester-based materials have been widely used in industrial production and daily life of people, and experts and scholars of various countries are continuously improving the technology, the polyester-based materials themselves still have some disadvantages. Such as a common polyester-based material: polycarbonate of bisphenol a type, which has good impact resistance, electrical properties and the like (senegan, meiyun, royal water and the like. research on the synthesis process of polycarbonate of bisphenol a type, Hubei chemical industry, 2002,4, 7); but still has some inherent physical or chemical defects, such as poor tolerance (ultraviolet light, acid-base, water, etc.), poor wear resistance (caused by low degree of polymerization), etc., which limits the wider application. Meanwhile, because the components of the material can react with other substances during the use process, some products harmful to human body or living environment can be generated, such as bisphenol A released by bisphenol A type PC during the use process, which has serious influence on the reproductive system of the body (Hunt, PA; Kara E.Koehler, Martha Susiaarjo, Craig A. Hodges, Arlene Ilagan, Robert C.Voigt, Sally Thomas, Brian F.Thomas and Terry J.Hassold.KL.Curr.Bio.2003, 13,546.; Howdeshell, Peterman PH, Judy BM, Taylor JA, Orazio CE, Ruhlen RL, Vom Saal FS, Welshons WV.environmental. health sport.2003, 111, 1180).

In addition, the development of new polymerization reactions and polymerization processes has been difficult, and therefore, the polymerization methods and production processes for polyesters have not been substantially improved, which has fundamentally limited the development and application of polyester-based materials. Meanwhile, with the continuous development of society and the continuous progress of science and technology, people begin to have higher requirements on polyester materials, such as no toxicity, better mechanical properties and the like. And the special fields, such as aerospace, electronic communication, microelectronics and the like, have higher requirements on materials. Therefore, it is one of the targets of the research and research of materials scientists to research and discover polyester materials with better overall performance, such as uniform polymerization degree, high purity, good tolerance (acid and alkali) and good wear resistance.

the development of novel polyester materials is an important direction of continuous efforts in the industry and academia, and Schrell research institute, Schrell, developed a series of sulfate (amine) polymers by bulk polymerization of sulfonyl fluoride monomers and methylsilyl-substituted monomers in organic base catalysts, (Angew. chem. int. Ed.2014, 53, 9466-. In addition, although the method can obtain various high-stability polysulfate (amine) polymers, the reaction process has high material cost, high viscosity in the later polymerization stage of the engineering process body, high energy consumption and no contribution to product industrialization, and the discharged materials need to be melted at high temperature for conveying.

disclosure of Invention

The invention aims to provide an economical and environment-friendly method for synthesizing a high-performance bisphenol type poly (amino) sulfate polymeric material, which can be applied to the synthesis of one-dimensional linear materials, and can provide a method for constructing a novel super-crosslinked planar two-dimensional or three-dimensional functional polymer material according to the design of monomer functionality, thereby greatly expanding the synthesis and application space of the material.

Another object of the present invention is to provide a polymeric bisphenol-based (urethane) sulfate material with high performance, which can solve the problems (e.g., stability) of the conventional polyester materials.

The invention discloses a synthesis method of a sulfuric acid (amine) ester linker polymer, which comprises the following steps:

carrying out polycondensation reaction on a hydroxyl-containing monomer or an amino-containing monomer and a sulfuryl fluoride monomer by a one-pot method under an alkaline condition, wherein,

The structural formula of the hydroxyl-containing monomer is HO-X (-OH) a, wherein X is a heterocyclic-containing aromatic compound, a non-heterocyclic-containing aromatic compound, aliphatic hydrocarbon, amino acid or amino acid derivative, a is an integer from 1 to 3,

the structural formula of the amino-containing monomer is H2N-Z (-NH2) b, wherein Z is a heterocyclic-containing aromatic compound, a non-heterocyclic-containing aromatic compound, aliphatic hydrocarbon, amino acid or an amino acid derivative, b is an integer from 1 to 3,

The sulfuryl fluoride monomer has a structural formula of FO2S-Y-SO2F, wherein Y is an aromatic compound, aliphatic hydrocarbon, amino acid or amino acid derivative.

In the synthesis method according to the present invention, in the sulfuryl fluoride monomer having the structural formula FO2S-Y-SO2F, Y is preferably an aromatic compound or a hydrocarbon compound containing at least one functional group selected from the group consisting of sulfonyl group, carbonyl group, amide, ether and heteroaryl group.

The synthetic method of the invention is characterized in that the hydroxyl-containing monomer is preferably a bisphenol monomer, the structural formula of the bisphenol monomer is preferably that of the sulfuryl fluoride monomer, R and R 'are the same or different, R and R' are preferably-S-, -O-, -CH2, -C (CH3)2, -C (CF3)2, -C (O) -, -S (O)2-, -C (O) NH-or-C (O) O-.

The synthesis method of the present invention, wherein the alkaline condition is preferably achieved by adding an inorganic base.

the synthesis method provided by the invention is characterized in that the molar ratio of the inorganic base to the sulfuryl fluoride monomer is preferably 0.5: 1-4: 1.

The synthesis method of the present invention, wherein the inorganic base is preferably at least one selected from the group consisting of potassium phosphate, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate and cesium carbonate.

The synthesis method of the present invention, wherein the polycondensation reaction preferably occurs in a solvent or in the absence of a solvent.

the synthesis method of the present invention, wherein the solvent is preferably at least one selected from the group consisting of sulfolane, N Dimethylformamide (DMF), N Dimethylacetamide (DEF), dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), chlorobenzene, xylene, trimethylbenzene, tetrahydrofuran, N-hexane, and cyclopentane, and the solvent preferably contains at least one water-carrying agent, and the water-carrying agent is preferably chlorobenzene, xylene, trimethylbenzene, or N-hexane.

The synthesis method according to the present invention is preferably such that, when the polycondensation reaction is carried out in the absence of a solvent, the polycondensation reaction is carried out in a state where the hydroxyl group-containing monomer or the amino group-containing monomer and the sulfuryl fluoride monomer are molten.

in the synthesis method of the present invention, it is preferable that the end-capping reaction or the terminal-modifying reaction is performed after the completion of the polycondensation reaction.

In the synthesis method of the present invention, the end-capping reagent in the end-capping reaction is preferably at least one selected from the group consisting of methyl chloride, phenol derivatives, and fluorobenzophenone monofunctional compounds.

The invention relates to a sulfuric acid (amine) ester linker polymer prepared by the synthesis method.

By the method, not only can one-dimensional linear high polymers (such as engineering plastics, electrolytes, thin film polymers and the like, but not limited to the applications) be constructed in a bifunctional polycondensation 2+2 mode, but also advanced planar and three-dimensional covalent amine sulfate ester materials (such as covalent organic porous energy storage, catalysis, separation and other materials or advanced device materials and the like, but not limited to the applications) can be constructed in a combined mode of 2+3 or 2+4 and the like, as shown in figure 12.

The one-dimensional linear material polycondensation can not be limited to two-component polycondensation, but also can carry out multi-component copolycondensation according to the material performance requirement (but at least 1 monomer containing bisphenol or alcohol and 1 sulfonyl fluoride monomer are required to carry out copolycondensation), and also comprises that the same monomer carries out self-polycondensation reaction polymerization at least with one phenol group and one sulfonyl fluoride group.

the sulfate (amine) ester linker polymer prepared by the synthesis method is preferably bisphenol type poly (amine) sulfate polymer, and the general formulA of the sulfate (amine) ester linker polymer can be briefly expressed as-A (-R-A) n-; a is SO2, nitrogen heteroaromatic ring, R is aromatic or aliphatic structure, n > is 1. The following structures can be classified according to the monomer structure:

Note: types A and B are aromatic rigid polymer chain segments, C and D are flexible aliphatic chain segments, E and F are aromatic and aliphatic alternating polycondensation chain segments, G is a self-polycondensation polymer chain segment, and H and I are bisphenol monomers and single aromatic ring polycondensation chain segments.

A-I all belong to one-dimensional polymer sulfuric acid (amine) ester materials, J and H are planar or three-dimensional covalent sulfuric acid (amine) ester materials constructed by the reaction of double-reaction functional groups and multi-reaction functional groups, and the materials can be porous materials or hyperbranched high polymer materials and have important application in the fields of electronic devices, separation and adsorption materials and the like;

Wherein, X2 and X1 may be the same or different, X1 and X2 may be heteroatoms such as S, O and N, and may also be C (when R1, R2, R1 ', R2' is CH3, the pure bisphenol a type high polymer material is obtained), X1(R1R1 '), and X2(R2R 2') may also be structures such as ketone and amide, and include specific substituted derivatives on the aromatic ring, and are not limited to the functional groups mentioned in the patent.

The synthetic method of the polymer containing the poly (amino) sulfate comprises the following steps: reacting the bisphenol protected by sulfonyl fluoride with bisphenol (or alcohol or amine) corresponding to the reaction functional group for 1 to 48 hours at 25 to 300 ℃ under the alkaline condition. The one-dimensional linear high polymer product obtained by the method is precipitated by a precipitating agent such as water (methanol or ethanol, isopropanol and the like) to obtain the poly (amino) sulfate polymer. If the material is a two-dimensional or three-dimensional material which is reacted by a multifunctional group, the material can be directly obtained by filtering and washing.

The chemical formula of the above polymerization method is shown below (IB: inorganic base):

when X2 ═ X1 and R2 ═ R1, R2 ═ R1 ', a ═ B'.

When X1 ═ X2 and R1 ═ R2, R1 ═ R2 ', a ═ B'.

When n2 ═ n1, and R7 ═ R5, R7 ═ R5 ', R8 ═ R6, R8 ═ R6', R10 ═ R9, R10 ═ R9 ', C ═ D'.

When n1 ═ n2, and R5 ═ R7, R5 ═ R7 ', R6 ═ R8, R6 ═ R8', R9 ═ R10, R9 ═ R10 ', D ═ C'.

When X ═ X1, and R ═ R1, R '═ R1', a; when X is X2 and R is R2 and R 'is R2', B.

when n-n 1-n 2, and R5-R7, R5 '-R7', R6-R8, R6 '-R8', R9-R10, R9 '-R10', D-C; when X ═ X1, and R ═ R1, R ' ═ R1 ', a '; when X is X2 and R is R2 and R ' is R2 ', B '.

When X ═ X1, and R ═ R1, R '═ R1', a; when X is X2 and R is R2 and R 'is R2', B.

When X ═ X1, and R ═ R1, R ' ═ R1 ', a '; when X is X2 and R is R2 and R ' is R2 ', B '.

When n is n1, C; when n is n2 and R5 is R7, R5 is R7 ', R6 is R8, R6 is R8 ', R9 is R10, R9 is R10 ', D.

when n is n1, C; when n is n2 and R5 is R7, R5 is R7 ', R6 is R8, R6 is R8 ', R9 is R10, R9 is R10 ', D.

in the above formulae, a, b, c, d, e, f, g, h, i, j, k is 1,2,3,4 … …;

n,n＝0,1,2……8；

R1, R1 ', R2, R2', R3, R3 ', R4, R4', R5, R5 ', R6, R6', R7, R7 ', R8, R8', R9, R9 ', R10, R10', R11, R12, R13, R14 are-Me (methyl), -Et (ethyl), -Ph (phenyl), -iPr (isopropyl), -H (hydrogen), or ═ O (double-bonded oxygen); r1, R1 ', R2, R2', R3, R3 ', R4, R4', R5, R5 ', R6, R6', R7, R7 ', R8, R8', R9, R9 ', R10, R10', R11, R12, R13 and R14 may be the same or different;

X1, X2 is-C (carbon), -Si (silicon), -S (sulfur) or-O (oxygen); x1 and X2 may be the same or different.

R15, R16 and R17 can be the same or different and can be groups such as hydrocarbons, amino acids, aldehydes, carboxylic acids, esters, even aromatic compounds and the like, however, if a porous material needs to be synthesized, R15, R16 and R17 are mostly short-chain structures so as to prevent the channels from being blocked by overlarge steric hindrance of the groups; r18 can be C or N, if N atom, it is usually used as flame retardant material, photoelectric material and other N-rich new materials.

R19 and R21 can be aromatics, hydrocarbons, amino acid derivatives, nitrogen heterocyclic compounds and the like.

r20 is C (carbon) or Si (silicon) element or a compound containing an adamantane tetrahedron structure.

The sulfonyl fluoride protected bisphenol has the following structural formula:

in the above formulae, R ', R5, R5', R6, R6 ', R9, R9', R11, R12, R13, and R14 are — Me (methyl), -Et (ethyl), -Ph (phenyl), -iPr (isopropyl), -H (hydrogen), or ═ O (doubly-bonded oxygen); r, R ', R5, R5', R6, R6 ', R9, R9', R11, R12, R13 and R14 can be the same or different;

X is-C (carbon), -Si (silicon), -S (sulfur) or-O (oxygen);

n＝0，1，2……8。

The synthesis reaction of the 4, 4-dihydroxy diphenyl-containing poly (amino) sulfate polymer can adopt two methods of solvent and solvent-free method. If the reaction is carried out in a solvent, the solvent may be sulfolane, N-methylpyrrolidone (NMP), N Dimethylformamide (DMF), N Dimethylacetamide (DMAC), Dimethylsulfoxide (DMSO), or the like; if the solvent-free condition is adopted, the bis-oxysulfonyl fluoride containing 4, 4-dihydroxydiphenyl and the bisphenol or diamine of 4, 4-dihydroxydiphenyl are fully melted at a certain temperature and then are subjected to polymerization reaction.

The polymerization reaction time can be regulated and controlled within 0.5-48 hours according to different raw material requirements and the presence or absence of a reaction solvent, and the polymerization degree of the product is regulated by adding a precipitator to terminate the reaction.

besides regulating the molecular weight by reaction time, a molecular weight regulator such as monophenol compounds, monooxyxanthyl fluoride compounds and the like can be added, or a blocking agent is added by adopting the reaction termination time, the blocking agent can be selected from compounds containing non-limiting reactive group halogen such as chloromethane, chlorosilane, F-substituted aromatic hydrocarbon and the like, or monophenol and alcohol compounds for blocking treatment, and a coupling agent, a functional group and the like can be added according to the requirements of the application direction and performance of the material to construct structural and functional materials.

The synthetic product of the invention is identified by nuclear magnetism, infrared spectrum, high resolution mass spectrum and the like, and is analyzed by gel chromatography, which shows that the target product, namely the poly (amino) sulfate polymer containing 4, 4-dihydroxy diphenyl is successfully synthesized.

Properties of bisphenol type polysulfate

1. physical property index

The bisphenol type polysulfate compound is a white or dark brown, transparent or semitransparent thermoplastic solid material.

The hydrocarbon polysulfate compound of the invention is a white, transparent or semitransparent thermoplastic solid material (the oligomer or star-shaped structure with small molecular weight presents gel or liquid state)

The three-dimensional or two-dimensional material is a solid insoluble material, can be directly obtained by filtration and washing, can be used as a composite membrane filler or other applications, and can be used as a separation material, an adsorption material and the like if the material is a material with high specific surface area.

2. index of chemical properties

The bisphenol type polysulfate compound has the polymerization degree of 10-1000, and has good alkali resistance and hydrolysis resistance.

The invention has the following beneficial effects:

Compared with the traditional polyester synthesis method, the method is economical, and the byproduct is fluoride inorganic salt which can be sold as an industrial product; the reaction condition is mild and easy to control, the reaction flow is simple, and the operation is easy; the post-treatment process is simple, the environmental pollution is small, and the method is favorable for industrial production. In addition, the synthesized bisphenol type polysulfate compound has excellent mechanical property, dielectric property, tolerance property and wear resistance, and compared with bisphenol A polycarbonate PC with the widest application, the bisphenol type polysulfate compound has the polymerization degree, the mechanical property, the tolerance property and the wear resistance which are far higher than those of the bisphenol A polycarbonate PC, and has wide application prospect in the fields of aviation, communication, electronics and microelectronic industries.

Drawings

FIG. 1 is a 1H-NMR spectrum of a bisphenol A type sulfuryl fluoride monomer;

FIG. 2 is a 13C-NMR spectrum of bisphenol A type sulfuryl fluoride monomer;

FIG. 3 is a schematic diagram showing the results of analyzing the purity of bisphenol A by HPLC;

FIG. 4 is a schematic diagram showing the results of HPLC analysis of bisphenol A type sulfuryl fluoride monomer;

FIG. 5 is a schematic diagram showing the HPLC analysis results of a diphenyl ether type sulfuryl fluoride monomer;

FIG. 6 is a 1H-NMR spectrum of PSE-1;

FIG. 7 is a 13C-NMR spectrum of PSE-1;

FIG. 8 is a schematic representation of the results of a TGA analysis of a PSE;

FIG. 9 is a schematic representation of the results of TGA and DSC analysis of PSE;

FIG. 10 is an FTIR analysis spectrum of PSE-1;

FIG. 11 is an FTIR analysis spectrum of BPA-B;

FIG. 12 shows the construction of one-dimensional linear high polymer, planar and three-dimensional stereo covalent amine sulfate materials;

FIG. 13 is a gel chromatography chart of example 1.

Detailed Description

The synthesis and properties of the 4, 4-dihydroxydiphenyl group-containing polysulfate compounds of the present invention will be further illustrated by the following specific examples.