US-12617900-B2 - Polymerization method for sulfate ester (amine) type linker polymer

Abstract

The present invention relates to a synthesis method for sulfate ester (amine) type linker polymer, which comprises a monomer containing hydroxyl or amino group and sulfuryl fluoride monomer proceeding a polycondensation reaction under a basic condition by one-pot process. As compared to the traditional polyester synthesis method, the present invention is economical; the reaction conditions are mild and easy to control, the reaction process is simple and easy to operate; the post-treatment process is simple with little environmental pollution, which is beneficial to industrial production. In addition, the bisphenol type polysulfate ester compounds synthesized by the present invention have excellent mechanical performances, dielectric performances, tolerance performances, and abrasion resistance performances.

Inventors

• Yunbin ZHOU

Assignees

• NEIMENGGU TUWEI NEW MATERIALS TECHNOLOGY CO., LTD.

Dates

Publication Date

20260505

Application Date

20190416

Priority Date

20180416

Claims (7)

1. 1 . A synthesis method for sulfate ester (amine) type linker polymer, consisting of: a monomer containing free hydroxyl group or free amino group and a monomer containing sulfuryl fluoride group proceeding a polycondensation reaction under a basic condition by one-pot process, wherein, the monomer containing free hydroxyl group has a structural formula of HO—X(—OH) n , wherein X is an aromatic group containing a heterocycle, an aromatic group containing no heterocycle, aliphatic hydrocarbon, amino acid, or amino acid derivative, and a is an integer of 1 to 3, the monomer containing free amino group has a structural formula of H 2 N—Z(—NH 2 ) b , wherein Z is an aromatic group containing a heterocycle, an aromatic group containing no heterocycle, aliphatic hydrocarbon, amino acid, or amino acid derivative, and b is an integer of 1 to 3, the monomer containing sulfuryl fluoride group has a structural formula of wherein R′ is —S—, —C(CF 3 ) 2 , —C(O)—, —C(O)NH—, or —C(O)O)—, wherein the basic condition is achieved by adding a base, and the base is an inorganic base, wherein the inorganic base and the monomer containing sulfuryl fluoride group have a molar ratio of 0.5:1-4:1, wherein the polycondensation reaction occurs in a presence or absence of solvent.
2. 2 . The synthesis method according to claim 1 , wherein the monomer containing free hydroxyl group is a bisphenol monomer having a structural formula of wherein R is —S—, —O—, —CH 2 , —C(CH 3 ) 2 , —C(CF 3 ) 2 , —C(O)—, —S(O) 2 —, —C(O)NH—, or —C(O)O—.
3. 3 . The synthesis method according to claim 1 , 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.
4. 4 . The synthesis method according to claim 1 , wherein the solvent is at least one selected from the group consisting of sulfolane, N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DEF), dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), chlorobenzene, xylene, trimethylbenzene, tetrahydrofuran, n-hexane, and cyclopentane, the solvent comprises at least one water-carrying agent, and the water-carrying agent is chlorobenzene, xylene, trimethylbenzene, or n-hexane.
5. 5 . The synthesis method according to claim 1 , wherein when the polycondensation reaction occurs in the absence of the solvent, and the polycondensation reaction proceeds in a state that the monomer containing free hydroxyl group or free amino group and the monomer containing sulfuryl fluoride group are molten.
6. 6 . The synthesis method according to claim 1 , wherein the synthesis method proceeds end-capping reaction or end modification reaction after the polycondensation reaction is complete.
7. 7 . The synthesis method according to claim 6 , wherein an end-capping reagent in the end-capping reaction is at least one selected from the group consisting of chloromethane, phenol, phenol-based derivatives, and chlorobenzophenone monofunctional compound.

Description

TECHNICAL FIELD The present invention belongs to the field of polymer material technology, and specifically, to sulfate ester (amine) type polymer by the polycondensation reaction of phenols or alcohols or amines and sulfonyl fluorides or sulfuryl fluorides under a basic condition. BACKGROUND With the continuous progress of science and technology, as one of the important chemical synthetic materials, polyester industry has made rapid development in recent years. At present, polyester materials have been widely used in the fields of fiber manufacturing, packaging, engineering plastics, electronics and electrical appliances, medical materials, construction, automotive, etc. In comparison, polyester materials have the following advantages: their syntheses are relatively simple and easy to control, the utilization rate of raw material monomers is high, their cost is more cheaper, and so on. Therefore, polyester materials have been widely used in industrial production and people's daily life. However, even though polyester materials have been widely used in industrial production and people's daily life, and experts and scholars in various countries are also constantly improving technology, polyester materials themselves still have some deficiencies. For example, a common polyester material: poly(bisphenol A) type PC, it has good resistance to impact, electrical performances, etc. (Zhi-gang ZHU, Fuming MEI, Shu WANG, etc. The Recent Progress in the Preparation of BPA Polycarbonates (PC), Hubei Chemical Industry, 2002, 4, 7); but it still has some inherent physical or chemical deficiencies, such as poor tolerance (UV, acid and base, water, etc.), poor abrasion resistance (caused by lower polymerization degree), etc. which limit its wider application. Meanwhile, as the material components may have some chemical reactions with other substances in the process of use, some harmful products on the human body or living environment may be generated, such as, bisphenol A released by bisphenol A type PC in the process of use will cause serious influence on the reproductive system of bodies (Hunt, PA; Kara E. Koehler, Martha Susiarjo, Craig A. Hodges, Arlene Ilagan, Robert C. Voigt, Sally Thomas, Brian F. Thomas and Terry J. Hassold. Curr. Bio. 2003, 13, 546; Howdeshell, K L; Peterman P H, Judy B M, Taylor J A, Orazio C E, Ruhlen R L, Vom Saal F S, Welshons W V. Environ. Health Perspect. 2003, 111, 1180). In addition, the developments of novel polymerization reaction and polymerization process have certain difficulties, thus no substantial improvements on the polymerization methods and production processes for polyester are made, which fundamentally limits the development and application of polyester materials. Meanwhile, with the continuous development of society and progress of science and technology, people begin to need polyester materials with higher standards, such as non-toxic, more excellent mechanical performances, etc. And some special fields, such as aeronautics & astronautics, electronic communications, microelectronics, etc., have higher requirements for the material. Therefore, research and discovery of polyester materials with comprehensive performances such as uniform polymerization degree, high purity, good tolerance (acid, base) and good resistance to abrasion, etc. is one of the goals that the materials scientists strive to study. The development of novel polyester type materials has been an important direction of industrial and academic endeavor, and Sharpless from Scripps Research Institute has developed a series of sulfate ester (amine) polymers by bulk polymerization in the presence of organic bases through the use of sulfonyl fluorine monomers and methyl silyl substituted monomers, (Angew. Chem. Int. Ed. 2014, 53, 9466-9470; Nat. Chem. 2017, 9, 1083-1088), wherein byproducts are methylsilyl alkyl fluorides, the current industrial use thereof is unknown, polluting the environment. In addition, although the method can obtain a variety of highly stable polysulfate ester (amine) polymers, however, the reaction process material cost is high, viscosity is higher at later stages of bulk polymerization in the engineering process, requiring a high temperature to melt and transport the material, energy consumption is high, which is not beneficial to the product industrialization. INVENTION SUMMARY The purpose of the present invention is to provide an economical and environmentally friendly synthesis method for high-performance bisphenol type polysulfate ester (amine) polymeric materials, which can be applied not only to synthesis of one-dimensional linear material, but also to provide a class of methods for constructing supercrosslinked planar two-dimensional or three-dimensional functional polymeric materials according to the design of monomer functionality, greatly expanding the synthesis and application space of the materials. Another purpose of the present invention is to provide a high-performance bisphen