Triaryl methyl onium ion compound and application thereof in degradation of polyester

Abstract

The invention relates to a triaryl methyl onium ion compound and application of the triaryl methyl onium ion compound in polyester degradation. Specifically disclosed is an application of a compound represented by a formula II in polyester degradation. The triaryl methyl onium ion compound provided by the invention meets one or two of the following effects and advantages: (1) the triaryl methyl onium ion compound can be recycled; and (2) the product separation is simple. # imgabs0 #

Description

[0001] This application claims the priority of Chinese patent application 202311299825.3, filed on October 9, 2023. This application cites the entire text of the above Chinese patent application. Technical Field

[0002] The invention relates to a triarylmethyl onium ion compound and application thereof in degrading polyester. Background Art

[0003] Polyester is a kind of polymer compound obtained by polycondensation of polyols and polycarboxylic acids, with excellent performance and wide applications. According to different polyester structures, it can be divided into polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyethylene 2,6-naphthalate (PEN), polyethylene 2,5-furan dicarboxylate (PEF), etc.

[0004] PET polyester has the advantages of high transparency, strong barrier properties, lightness and durability, and is widely used in food packaging, textiles, films, etc. The demand for PET is growing, but due to its slow degradation rate in the natural environment, the accumulation of waste PET has brought serious environmental pollution. Therefore, the recycling of PET is of great significance. At present, the recycling methods of PET polyester mainly include mechanical recycling, chemical recycling, and enzyme-catalyzed degradation. The chemical recycling method can obtain polyester monomers or intermediates and use them as raw materials to re-prepare high-performance polyester materials, which overcomes the shortcomings of limited application scope due to reduced product performance and high enzyme breeding costs, and is an important research field for scientific researchers.

[0005] At present, the main chemical degradation methods of PET are alcoholysis, hydrolysis and ammonolysis. Alcoholysis uses alcohol compounds such as methanol or ethylene glycol as degradation agents, and uses different processes to degrade PET into methyl terephthalate (DMT) or bis(2-hydroxyethyl) terephthalate (BHET) and ethylene glycol. The aromatic ester products obtained by alcoholysis have high purity and can be used as monomers for polymers. For example, Teijin's low-pressure alcoholysis process: This process first cuts PET polyester into pieces and adds it to ethylene glycol, uses 0.1-10% sodium carbonate or zinc acetate as a catalyst, and reacts at 175-190°C and 0.1-0.5MPa for 1-10 hours. The resulting mixture is then added to methanol and treated with an ester transfer catalyst to obtain DMT. After recrystallization, centrifugal separation and other treatments, high-purity DMT can be obtained. The alcoholysis process is relatively mature and often involves high temperature or low pressure control. The hydrolysis method is to catalyze the degradation of PET polyester with water as solvent to obtain monomers of terephthalic acid (TPA) and ethylene glycol. The obtained monomers can be directly used for the reproduction of PET polyester. The neutral hydrolysis method is usually carried out in the temperature range of 200-300°C, and the pressure is usually controlled between 1 and 4 MPa. For example, the process of hydrolyzing PET developed by Celanese. The alkaline hydrolysis method is usually carried out in an aqueous solution of 4-20wt% sodium hydroxide or potassium hydroxide. This method requires acidification post-treatment to obtain high-purity terephthalic acid, which increases the operating cost. The acid hydrolysis method requires the use of excessive concentrated sulfuric acid, and the reaction process will corrode the reactor and produce a large amount of wastewater pollution. The amine hydrolysis method is to react PET polyester with different types of amines to generate the corresponding benzamide. Due to the narrow application range of the amine hydrolysis product, the amine hydrolysis method has not yet been industrialized.

[0006] The existing PET chemical recycling methods face the limitations of harsh reaction conditions, low recycling efficiency, low product purity, and complex post-processing. Therefore, it is urgent to develop a mild, efficient, green and sustainable polyester degradation method. Summary of the invention

[0007] The technical problem to be solved by the present invention is to overcome the defects of the existing polyester degradation methods such as harsh conditions, high energy consumption or complex product separation, and provide triarylmethyl onium ion compounds and their application in degrading polyester. The triarylmethyl onium ion compounds of the present invention meet one or more of the following effects and advantages: (1) when used for catalytic degradation of polyester, the triarylmethyl onium ion compounds can be recycled and reused; (2) product separation is simple; the application of the degraded polyester of the present invention meets one or more of the following effects and advantages: (1) the obtained degradation product diol dicarboxylate can be converted into diol by conventional methods for polyester resynthesis or directly used for polyester resynthesis, or directly used as a chemical for other chemical conversions; (2) it is conducive to maximizing the industrial benefits of polyester degradation.

[0008] The present invention solves the above technical problems through the following technical solutions.

[0009] The present invention provides an application of a compound as shown in formula II in degrading polyester;

[0010]

[0011] wherein l, m and p are each independently 0, 1 or 2;

[0012] It is an anion;

[0013] Each R 1 , R 2 and R 3 Each is independently halogen, C1-C6 alkyl, C1-C6 alkoxy, C6-C 10 Aryl or one or more R 1-1 Substituted C6-C 10 Aryl;

[0014] or, for

[0015] m 1 and p 1 Each is independently 0 or 1;

[0016] Each R 1-1 Each independently C1-C6 alkoxy or one or more R 1-1-1 Substituted C1-C6 alkoxy;

[0017] q is 1, 2, or 3;

[0018] R a , R b and R c Each is independently a C1-C6 alkyl group;

[0019] For halide ions or BF4 - ;

[0020] Each R 1-1-1 Each is independently -SO3H.

[0021] In certain preferred embodiments of the present invention, certain groups and degradation conditions in the application of the compound as shown in Formula II in the degradation of polyester are defined as follows, and the unmentioned groups and degradation conditions are the same as those described in any embodiment of the present invention (referred to as "in certain embodiments of the present invention").

[0022] In certain embodiments of the present invention, R1 , R 2 and R 3 wherein the halogen is independently fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine.

[0023] In certain embodiments of the present invention, R 1 , R 2 and R 3 In the above, the C1-C6 alkyl groups are independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl, preferably methyl or ethyl, more preferably methyl.

[0024] In certain embodiments of the present invention, R 1 , R 2 and R 3 In the above, the C1-C6 alkoxy groups are independently methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy or tert-butoxy, preferably methoxy.

[0025] In certain embodiments of the present invention, R 1 , R 2 and R 3 In the C6-C 10 The aryl groups are each independently phenyl or naphthyl; preferably phenyl.

[0026] In certain embodiments of the present invention, R 1-1 In the above, the C1-C6 alkoxy group is methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy or tert-butoxy, preferably n-propoxy.

[0027] In certain embodiments of the present invention, R a , R b and R c wherein the C1-C6 alkyl groups are independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl, preferably methyl or n-propyl.

[0028] In certain embodiments of the present invention, R 1-1 In the embodiment, the halide ion is a halogen anion, preferably F - , Cl - Br - or I - For example, - .

[0029] In certain embodiments of the present invention, It is a conventional anion in the art, preferably tetrakis(pentafluorophenyl)borate ion.

[0030] In certain embodiments of the invention, l is 0, 1 or 2.

[0031] In certain embodiments of the present invention, m is 0, 1 or 2.

[0032] In certain embodiments of the present invention, p is 0, 1 or 2.

[0033] In certain embodiments of the invention, each R 1 , R 2 and R 3 Each independently is a C1-C6 alkyl group or is replaced by one or more R 1-1 Substituted C6-C 10 Aryl; or for

[0034] Preferably C1-C6 alkyl or one or more R 1-1 Substituted C6-C 10 Aryl; or for

[0035] In certain embodiments of the present invention, m 1 Is 0 or 1.

[0036] In certain embodiments of the present invention, p 1 Is 0 or 1.

[0037] In certain embodiments of the invention, each R 1-1 Each independently or one or more R 1-1-1 Substituted C1-C6 alkoxy.

[0038] In certain embodiments of the present invention, l, m and p are each independently 0, 1 or 2;

[0039] It is an anion;

[0040] Each R 1 , R 2 and R 3 Each independently is a C1-C6 alkyl group or is replaced by one or more R 1-1 Substituted C6-C 10 Aryl; or for

[0041] Preferably, it is C1-C6 alkyl or is replaced by one or more R 1-1 Substituted C6-C 10 Aryl; or for

[0042] m 1 and p1 Each is independently 0 or 1;

[0043] Each R 1-1 Each independently or one or more R 1-1-1 Substituted C1-C6 alkoxy;

[0044] q is 1, 2, or 3;

[0045] R a and R c Each is independently a C1-C6 alkyl group;

[0046] Each R 1-1-1 Each is independently -SO3H.

[0047] In certain embodiments of the present invention, R 1 is fluorine, chlorine, bromine, methyl, ethyl, methoxy, phenyl,

[0048] In certain embodiments of the present invention, R 2 is fluorine or methyl.

[0049] In certain embodiments of the present invention, R 3 for In certain embodiments of the present invention, for

[0050] In certain embodiments of the present invention, for In certain embodiments of the present invention, the compound as shown in Formula II is any of the following structures:

[0051]

[0052] The anions in compounds C1-C20 are all tetrakis(pentafluorophenyl)borate ions.

[0053] In certain embodiments of the present invention, the application is Scheme 1 or Scheme 2:

[0054] Scheme 1 comprises the following steps: degrading polyester in water under the action of a compound as shown in Formula II; the polyester comprises repeating units formed by a dicarboxylic acid and a diol;

[0055] Scheme 2 comprises the following steps: in carboxylic acid, under the action of a compound as shown in Formula II, degrading the polyester; the polyester comprises repeating units formed by a dicarboxylic acid and a diol;

[0056]

[0057] Among them, l, m, p, R 1 , R 2 , R 3 and The definitions are as mentioned above.

[0058] In certain embodiments of the present invention, the structure of the repeating unit may be as shown in Formula I:

[0059]

[0060] Among them, ring A is C6-C 10 An aromatic ring or a 5-6-membered heteroaromatic ring; in the 5-6-membered heteroaromatic ring, the heteroatom is selected from one or more of N, O and S, and the number of the heteroatom is 1 or 2;

[0061] n is an integer from 1 to 9.

[0062] In certain embodiments of the present invention, in ring A, the C6-C 10 The arylene ring may be a phenylene ring (e.g. ) or a naphthylene ring.

[0063] In certain embodiments of the present invention, in ring A, in the 5-6 membered heteroaromatic ring, the heteroatom is O, and the number of the heteroatoms is 1 or 2.

[0064] In certain embodiments of the present invention, in ring A, the 5-6 membered heteroaromatic ring may be a furan ring; for example

[0065] In certain embodiments of the present invention, n may be an integer of 1-5, and may be 1, 2 or 3.

[0066] In certain embodiments of the present invention, Ring A may be

[0067] In certain embodiments of the present invention, the molecular weight of the repeating unit may be 2,000 to 500,000, preferably 20,000 to 30,000.

[0068] In certain embodiments of the present invention, η of the repeating unit may be 0.5 to 2 dL / g, preferably 0.6 to 1.2 dL / g, for example 0.89 dL / g or 1.11 dL / g.

[0069] In certain embodiments of the present invention, the structure of the repeating unit may be

[0070] In certain embodiments of the present invention, the structure of the repeating unit may be η is 0.89 dL / g.

[0071] In certain embodiments of the present invention, the structure of the repeating unit may be η is 1.11dL / g.

[0072] In certain embodiments of the present invention, the structure of the repeating unit may be η is 0.65-0.95dL / g.

[0073] In certain embodiments of the present invention, the structure of the repeating unit may be η is 0.65-0.95 dL / g; preferably 0.8 dL / g.

[0074] In certain embodiments of the present invention, the repeating unit of the polyester may be a structure as shown in Formula I:

[0075]

[0076] Wherein, ring A and n are as defined above.

[0077] In certain embodiments of the present invention, in Scheme 1, the mass volume ratio of the polyester to the water may be 30 g / L to 480 g / L; preferably 40 g / L to 300 g / L; for example 48 g / L, 96 g / L or 240 g / L.

[0078] In certain embodiments of the present invention, in Scheme 1, the molar ratio of the compound represented by Formula II to the polyester may be 5% to 50%, preferably 10% to 35%, for example 20% or 28%.

[0079] In certain embodiments of the present invention, in Scheme 1, the degradation temperature may be 100-150°C, such as 100°C or 120°C.

[0080] In certain embodiments of the present invention, in Scheme 1, the degree of degradation can be monitored by conventional means in the art (such as infrared spectroscopy, mass spectrometry, nuclear magnetic resonance, etc.), and the degradation time can be 8 to 96 hours, such as 24 hours, 48 ​​hours or 72 hours.

[0081] In certain embodiments of the present invention, in Scheme 1, the water, the compound represented by Formula II and the polyester are mixed and then degraded; the degradation temperature is preferably 100-120°C.

[0082] In certain embodiments of the present invention, the scheme 1 may further include the following post-treatment steps: filtering; washing the solid obtained by filtration to obtain a dicarboxylic acid.

[0083] In certain embodiments of the present invention, in the post-treatment step of Scheme 1, the washing solvent may be water and a halogenated alkane solvent; the halogenated alkane solvent is preferably dichloromethane.

[0084] In certain embodiments of the present invention, the scheme 1 may further include the following post-treatment step: removing the solvent from the filtrate obtained in the filtration step and the washing liquid obtained after washing to obtain a diol.

[0085] In certain embodiments of the present invention, in the post-treatment step of Scheme 1, the removal of the solvent from the filtrate obtained in the filtration step and the washing liquid obtained after washing can be carried out by evaporation and concentration.

[0086] In certain embodiments of the present invention, in Scheme 2, the carboxylic acid may be a C2-C6 carboxylic acid, preferably acetic acid, n-propionic acid or n-butyric acid; more preferably acetic acid.

[0087] In certain embodiments of the present invention, in Scheme 2, the mass volume ratio of the polyester to the carboxylic acid may be 60 g / L to 960 g / L; preferably 160 g / L to 720 g / L; for example 240 g / L, 460 g / L, 480 g / L or 680 g / L.

[0088] In certain embodiments of the present invention, in Scheme 2, the molar ratio of the compound as shown in Formula II to the polyester may be 1% to 50%; preferably 5% to 40%; more preferably 8% to 30%; for example 10% or 20%.

[0089] In certain embodiments of the present invention, in Scheme 2, the degradation temperature may be 100-180°C, such as 120°C or 150°C.

[0090] In certain embodiments of the present invention, in Scheme 2, the degree of degradation can be monitored by conventional means in the art (such as infrared spectroscopy, mass spectrometry, nuclear magnetic resonance, etc.), and the degradation time can be 6 to 24 hours, such as 8 hours, 10 hours or 12 hours.

[0091] In certain embodiments of the present invention, in Scheme 2, the carboxylic acid, the compound represented by Formula II and the polyester are mixed and then degraded; the degradation temperature is preferably 120-150°C.

[0092] In certain embodiments of the present invention, Scheme 2 may further include the following post-treatment steps: filtering; washing the solid obtained by filtration to obtain a dicarboxylic acid.

[0093] In certain embodiments of the present invention, in the post-treatment step of Scheme 2, the washing solvent may be a halogenated alkane solvent; the halogenated alkane solvent is preferably dichloromethane.

[0094] In certain embodiments of the present invention, the scheme 2 may further include the following post-treatment step: removing the solvent from the filtrate obtained in the filtering step and the washing liquid obtained after washing to obtain diol dicarboxylic acid ester or diol.

[0095] The present invention also provides a method for degrading polyester, which is the following scheme 1 or scheme 2:

[0096] Scheme 1 comprises the following steps: degrading polyester in water under the action of a compound as shown in Formula II; the polyester comprises repeating units formed by a dicarboxylic acid and a diol;

[0097] Scheme 2 comprises the following steps: in carboxylic acid, under the action of a compound as shown in Formula II, degrading the polyester; the polyester comprises repeating units formed by a dicarboxylic acid and a diol;

[0098]

[0099] Among them, l, m, p, R 1 , R 2 , R 3 and The definitions of are as mentioned above;

[0100] The raw materials, conditions and operations in Scheme 1 and Scheme 2 are the same as described above.

[0101] The present invention also provides a compound as shown in Formula II:

[0102]

[0103] Among them, R 1 , R 2 , R 3 , l, m and p are defined as above;

[0104] The compound shown in formula II is not

[0105] Unless otherwise specified, the terms used in the present invention have the following meanings:

[0106] The term "polyester" refers to a polymer in which repeating units are connected by ester functional groups. The repeating units of "polyester" may be ester structures formed by dicarboxylic acids and diols.

[0107] Examples of "polyesters" include, but are not limited to, polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyethylene terephthalate co-isosorbide terephthalate (PEIT), polylactic acid (PLA), poly(L-lactic acid) (PLLA), poly(D-lactic acid) (PDLA), poly(D,L-lactic acid) (PDLLA), stereocomplex PLA (scPLA), polyhydroxyalkanoate (PHA), poly( 3-hydroxybutyrate) (P(3HB) / PHB), poly(3-hydroxyvalerate) (P(3HV) / PHV), poly(3-hydroxyhexanoate) (P(3HHx)), poly(3-hydroxyoctanoate) (P(3HO)), poly(3-hydroxydecanoate) (P(3HD)), poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (P(3HB-co-3HV) / PHBV), poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (P(3HB-co-3HHx ) / (PHBHHx)), poly(3-hydroxybutyrate-co-4-hydroxybutyrate) (P(3HB-co-4HB)), poly(3-hydroxybutyrate-co-5-hydroxyvalerate) (PHB5HV), poly(3-hydroxybutyrate-co-3-hydroxypropionate) (PHB3HP), polyhydroxybutyrate-co-hydroxyoctanoate (PHBO), polyhydroxybutyrate-co-hydroxyoctadecanoate (PHBOd), poly(3-hydroxybutyrate-co-3-hydroxyvalerate-co-4-hydroxybutyrate) ester) (P(3HB-co-3HV-co-4HB)), polybutylene succinate (PBS), polybutylene succinate-co-butylene adipate (PBSA), polybutylene adipate-co-butylene terephthalate (PBAT), polyethylene furandicarboxylate (PEF), polycaprolactone (PCL), poly(ethylene adipate) (PEA) and blends / mixtures of two or more of the above, and also covers polyester segments in copolymers such as polyurethane (PU) and unsaturated polyester resins.

[0108] The term "polymer" refers to a macromolecule whose structure is composed of a plurality of repeating units linked by covalent chemical bonds. In the context of the present invention, the term polymer encompasses natural and synthetic polymers composed of a single type of monomer (i.e., homopolymers) or natural and synthetic polymers composed of two or more different types of monomers (i.e., copolymers).

[0109] Without violating the common sense in the art, the above-mentioned preferred conditions can be arbitrarily combined to obtain the preferred embodiments of the present invention.

[0110] The reagents and raw materials used in the present invention are commercially available.

[0111] The positive and progressive effects of the present invention are: the triarylmethyl onium ion compound of the present invention satisfies one or two of the following advantages: (1) when used for catalytic degradation of polyester, the triarylmethyl onium ion compound can be recycled and reused; (2) the product separation is simple;

[0112] The application of the degraded polyester of the present invention satisfies one or more of the following advantages: (1) mild reaction conditions; (2) no need for complex conditions such as high temperature and high pressure; (3) high conversion rate; (4) simple separation of the obtained product; (5) wide application range; (6) the catalyst can be reused repeatedly; (7) in some schemes, water is used as a green solvent and the conditions are mild; (8) the obtained degradation product diol dicarboxylic acid ester can be converted into diol by conventional methods for resynthesis of polyester or directly used for resynthesis of polyester, or directly used as a chemical for other chemical conversions; (9) it is conducive to maximizing the industrial benefits of polyester degradation. DETAILED DESCRIPTION

[0113] The present invention is further described below by way of examples, but the present invention is not limited to the scope of the examples. The experimental methods in the following examples without specifying specific conditions are carried out according to conventional methods and conditions, or selected according to the product specifications.

[0114]

[0115] The anions in compounds C1-C20 are all tetrakis(pentafluorophenyl)borate ions.

[0116] Preparation and characterization of catalysts

[0117] Catalyst preparation method 1 (GP1)

[0118] Under nitrogen protection, add KB(C6F5)4 (1.0 eq.), triarylmethylchloromethane (1.0 eq.), and dichloromethane (0.05 mol / L) into a round-bottom flask and stir at room temperature for 1 hour. Remove the insoluble KCl by passing through diatomaceous earth, and remove the excess solvent by rotary evaporation. Recrystallize to obtain the product.

[0119] Catalyst Preparation Method 2 (GP2)

[0120] Dissolve KB(C6F5)4 (1.0 eq.) in ether (0.2 mol / L) and pass through an Amberlyst 15 ion exchange column to obtain an ether solution of HB(C6F5)4. Dissolve the corresponding polyaryl carbinol in ether, cool to 0°C, and slowly drop the HB(C6F5)4 solution into the ether with sufficient stirring. After addition, return to room temperature. Recrystallize to obtain the product.

[0121] Preparation of Aromatic Ketones (GP3)

[0122] Add 4-bromobenzoylbenzene (or 3-bromofluorene-9-one) (1.0 eq.), aryl borate (or aryl pinacol ester) (1.5 eq.), tetrakistriphenylphosphine palladium (0.1 eq.), potassium carbonate (1.5 eq.) to a round-bottom flask. Add 1,2-dimethoxyethane and water (v / v=10:1, 0.1 mol / L), reflux at 85°C for 6 hours. Cool to room temperature, quench with saturated ammonium chloride solution, extract with ethyl acetate, evaporate under reduced pressure, and purify the residue by silica gel column chromatography to obtain the corresponding aromatic ketone.

[0123] Preparation of polyaryl carbinols (GP4)

[0124] In a dry round-bottom flask, the corresponding polyaryl ketone (1.0 eq.) was dissolved in tetrahydrofuran (1.0 mol / L), and the aryl Grignard reagent (1.2 eq.) was slowly added dropwise at 0°C. After the addition was completed, the temperature was slowly raised to room temperature. TLC monitoring was performed, and after the reaction was completed, the reaction was quenched with a saturated ammonium chloride solution in an ice bath, extracted with ethyl acetate, and evaporated under reduced pressure. The residue was separated and purified by silica gel column chromatography to obtain the corresponding polyaryl methanol.

[0125] Preparation of Polyaryl Methyl Chloroalkanes (GP5)

[0126] The corresponding polyaryl carbinol (1.0 eq.) was dissolved in toluene (1.5 mol / L) in a round three-necked flask and heated under reflux. Acetyl chloride (2.8 eq.) was added to the round three-necked flask through a constant pressure dropping funnel, and the reaction was continued for about 30 minutes. Water was added to quench the reaction under ice bath, and the reaction was performed by extraction with ethyl acetate and vacuum rotary evaporation. The residue was separated and purified by silica gel column chromatography to obtain the corresponding triaryl methyl chloroalkane.

[0127] Preparation of ammonium tetrafluoroborate (GP6)

[0128] Add polyaryl carbinol (1.0 eq.) and dichloromethane (0.4 mol / L) into a flask. Add trimethyloxonium tetrafluoroborate (1.3 eq.) dropwise at room temperature and stir to react overnight. Remove dichloromethane by rotary evaporation, add ether, filter the resulting solid and rinse with ether to obtain ammonium tetrafluoroborate.

[0129] Preparation of Sulfonic Acid Ammonium Salt (GP7)

[0130] Polyaryl carbinol (1.0 eq.), 1,3-propane sultone (1.0 eq.), and toluene (1.25 mol / L) were added to a round-bottom flask and stirred overnight at 90° C. The obtained solid was filtered and dried to obtain ammonium sulfonate salt.

[0131] Preparation of ammonium iodide salt (GP8)

[0132] Add polyaryl carbinol (1.0 eq.) and dichloromethane (0.4 mol / L) into a flask. Add iodomethane (1.0 eq.) dropwise at room temperature and stir to react overnight. Remove dichloromethane by rotary evaporation, add ether, filter the resulting solid and dry it to obtain ammonium iodide salt.

[0133] Preparation of Sodium Sulfonate (GP9)

[0134] Phenol (1.0 eq.) was added to a sodium hydroxide aqueous solution (1.0 eq., 2.5 M), and a 1,4-dioxane solution (1.0 eq., 1.25 M) of 1,3-propane sultone was added dropwise thereto. The mixture was stirred at room temperature for 12 hours. After the reaction was completed, the solution was dried by rotary evaporation to obtain a sodium sulfonate solid.

[0135] C1, C3, C4, C5, C6, C8 were prepared according to GP1.

[0136]

[0137] C3: orange solid, 95% yield. 1 H NMR (400MHz, CDCl3) δ8.29(tt,J=7.5,1.4Hz,2H),7.94(td,J=7.8,1.7Hz,1H),7.84(t,J=7.6Hz,4H),7.78( dd,J=8.1,1.1Hz,1H),7.69(dt,J=7.1,1.4Hz,4H),7.60(td,J=7.6,1.1Hz,1H),7.25(dd,J=7.7,1.7Hz,1H). 19 F NMR (376MHz, CDCl3) δ-132.95 (m), -162.88 (t, J = 20.8Hz), -166.72 (t, J = 21.8Hz). 13 C NMR (126MHz, CDCl3) δ209.6,149.0,147.1,146.0,143.1,141.0,140.6,140. 5,140.4,138.6,137.1,133.0,131.4,129.6,128.4,127.9,126.5.HR-MS(ESI + ) Calculated value C 19 H 14 Cl + m / z[M] + 277.0779; measured value 277.0778.

[0138] C4: orange solid, 479 mg, 50% yield. 1H NMR (400MHz, CDCl3) δ8.30 (t, J = 7.4Hz, 2H), 7.96 (td, J = 7.8, 1.6Hz, 1H), 7.85 (t, J = 7. 6Hz,4H),7.81–7.76(m,1H),7.69(dt,J=7.1,1.4Hz,4H),7.61(td,J=7.7,1.0Hz,1H). 13 C NMR (126MHz, CDCl3) δ162.5,149.1,147.2,143.5,139.5,137.3,135.4,130.8,130.8,129.3,128.5,126.6,68.7,55.3. 19 F NMR(376MHz, CDCl3)δ-80.64,-116.64,-132.76–-133.03(m),-162.68(t,J=20.6Hz).HR-MS(ESI + ) Calculated value C 19 H 13 F2 + m / z[M] + 279.0980; measured value 279.0929.

[0139] C5: yellow solid, 98% yield. 1 H NMR (500MHz, CDCl3) δ8.16(t,J=7.5Hz,2H),7.79(t,J=7.7Hz,4H),7.65(d,J=8.0Hz,2H),7.56(t,J=8.9Hz,6H),2.70(s,3H). 13 C NMR (126MHz, CDCl3) δ208.1,160.3,149.1,147.1,143.2,142.3,141.4,139.6,137.7,135.2,132.1,130.3,23.3. 19 F NMR(376MHz, CDCl3)δ-132.6,-163.0(t,J=20.4Hz),-166.8(t,J=20.7Hz).HR-MS(ESI + ) Calculated value C 20 H 17 + m / z[M] + 257.1325; measured value 257.1321.

[0140] C6: orange solid, 97% yield. 1H NMR (500MHz, CDCl3) δ8.05(t,J=7.5Hz,2H),7.77–7.69(m,6H),7.50–7.45(m,4H),7.29(d,J=9.3Hz,2H),4.20(s,3H). 13 C NMR (101MHz, CDCl3) δ200.0,175.9,149.3,147.1,146.9,139.1,137.4,135.0,133.3,129.9,128.0,127.8,118.2,58.0. 19 F NMR(471MHz, CDCl3)δ-132.52,-162.95(t,J=20.5Hz),-166.75(t,J=18.7Hz).HR-MS(ESI + ) Calculated value C 20 H 17 O + m / z[M] + 273.1274; measured value 273.1271.

[0141] C8: 1 H NMR (500MHz, CDCl3) δ8.11(t,J=7.5Hz,1H),7.76(t,J=7.7Hz,2H),7.62(d,J=8.0Hz,4H),7.52(dd,J=17.2,7.8Hz,6H),2.68(s,6H). 13 C NMR (126MHz, CDCl3) δ206.1,158.5,149.2,147.3,142.3,141.4,140.8,139.5,137.5,137.2,135.3,131.8,130.2,23.2. 19 F NMR(471MHz, CDCl3)δ-132.3,-161.5,-166.0.

[0142] Preparation of C2, C7, C9-14: Prepare polyaryl methyl alcohols C2-S1, C7-S1, C9-S1 to C14-S1 according to GP4; then prepare C2, C7, C9-14 according to GP2.

[0143]

[0144] In the above reaction formula, "overnight" means: overnight.

[0145] C2-S1: white solid, 95% yield. 1H NMR (400MHz, CDCl3) δ7.43 (d, J = 8.6 Hz, 2H), 7.32 (d, J = 7.5 Hz, 6H), 7.25 (d, J = 8.0 Hz, 5H), 7.18 (d, J = 8.6 Hz, 2H), 2.80 (s, 1H). 13 CNMR (101MHz, CDCl3) δ146.5,146.0,131.1,129.9,128.2,127.9,127.7,121.5,81.9.

[0146] C2: yellow solid, 80% yield. 1 H NMR (500MHz, CDCl3) δ8.26(t,J=7.5Hz,2H),8.01(d,J=8.2Hz,2H),7.84(t,J=7.7Hz,4H),7.61(d,J=7.7Hz,4H),7.44(d,J=8.3Hz,2H). 13 CNMR(101MHz, CDCl3)δ146.4,143.3,131.4,131.0,129.7,129.4,128.5,128.1,127.8,127.6,126.6,121.4,65.9.HR-MS(ESI + ) Calculated value C 19 H 14 Br + m / z[M] + 321.0273; Measured value 321.0271.

[0147] C7-S1: colorless viscous liquid, 45% yield. 1 H NMR (400MHz, CDCl3) δ7.28(q,J=7.5,6.9Hz,10H),7.11–7.03(m,2H),6.91(d,J=7.9Hz,1H),2.77(s,1H),2.25(s,3H),2.21(s,3H). 13 CNMR(101MHz, CDCl3)δ147.2,144.6,136.3,135.8,129.2,129.1,128.0,128.0,127.3,125.6,82.0,20.1,19.5.

[0148] C7: yellow solid, 95% yield. 1H NMR (400MHz, CDCl3) δ8.15(tt,J=7.5,1.3Hz,2H),7.79(t,J=7.7Hz,4H),7.62(d,J=8. 6Hz,1H),7.55(d,J=7.7Hz,4H),7.41(dt,J=3.9,2.0Hz,2H),2.62(s,3H),2.41(s,3H). 13 C NMR (101MHz, CDCl3) δ207.5,159.8,149.3,146.8,143.3,142.0,141.6,141.2,140.9,139.6,138.4,137.2,134.9,132.6,130.2,21.9,19.6. 19 F NMR(376MHz, CDCl3)δ-132.47–-132.72(m),-163.02(t,J=20.5Hz),-166.80(t,J=20.1Hz).HR-MS(ESI + ) Calculated value C 21 H 19 + m / z[M] + 271.1481; measured value 271.1478.

[0149] C8: yellow solid, 98% yield. 1 H NMR (500MHz, CDCl3) δ8.11(t,J=7.5Hz,1H),7.76(t,J=7.7Hz,2H),7.62(d,J=8.0Hz,4H),7.52(dd,J=17.2,7.8Hz,6H),2.68(s,6H). 13 CNMR (126MHz, CDCl3) δ206.1,158.5,149.2,147.3,142.3,141.4,140.8,139.5,137.5,137.2,135.3,131.8,130.2,23.2. 19 F NMR (471MHz, CDCl3) δ-132.36 (d, J = 19.0Hz), -161.54 (tt, J = 32.9, 19.8Hz), -165.97 (d, J = 23.9Hz). HR-MS (ESI + ) Calculated value C 21 H 19 + m / z[M] + 271.1481; measured value 271.1476.

[0150] C9-S1: white solid, 92% yield. 1 H NMR (400MHz, CDCl3) δ7.59(dd,J=7.7,1.6Hz,2H),7.57–7.53(m,2H),7.43(t,J=7.6Hz,2H),7.38–7.26(m,13H),2.83(s,1H). 13 C NMR (101MHz, CDCl3) δ146.9,146.0,140.8,140.2,128.9,128.5,128.1,128.1,127.5,127.2,126.8,82.1.

[0151] C9: 1 H NMR (500MHz, CDCl3) δ8.14 (dt, J=19.2, 6.9Hz, 4H), 7.83 (dt, J=15.4, 6.9

[0152] Hz, 6H), 7.76 (d, J = 7.4Hz, 2H), 7.62 (p, J = 5.8, 5.2Hz, 7H). 19 F NMR (471MHz, CDCl3) δ -133.3 (d, J = 17.7Hz), -162.2 (t, J = 20.6Hz), -166.5 (t, J = 19.6Hz).

[0153] C10-S1: white solid, 99% yield. 1 H NMR (400MHz, CDCl3) δ7.65(dd,J=7.6,1.0Hz,2H),7.39–7.28(m,6H),7.28–7.17(m,5H),2.43(d,J=4.1Hz,1H). 13 C NMR (101MHz, CDCl3) δ150.6,143.3,139.7,129.2,128.6,128.4,127.4,125.5,124.9,120.2,83.7.

[0154] C10: white solid, 80% yield. 1 H NMR (500MHz, CDCl3) δ7.81(d,J=7.6Hz,1H),7.38(t,J=7.4Hz,2H),7.32(d,J=7.5Hz,2H),7.27(d,J=6.0Hz,6H),7.11–7.07(m,2H). 13CNMR (126MHz, CDCl3)δ149.1,147.9,147.2,141.0,137.3,135.3,128.7,128.4,127.3,126.8,125.4,119.9,68.4.None 200 19 F NMR(471MHz, CDCl3)δ-132.83(q,J=10.4,10.0Hz),-162.78(t,J=20.4Hz),-166.83(t,J=19.6Hz).HR-MS(ESI + ) Calculated value C 20 H 15 + m / z[M] + 255.1168; Found 255.1165.HR-MS (ESI + ) Calculated value C 19 H 13 + m / z[M] + 241.1012; measured value 241.1009.

[0155] C11-S1: pale yellow solid, 97% yield. 1 H NMR (400MHz, CDCl3) δ7.71(d,J=7.6Hz,2H),7.45–7.31(m,6H),7.29(d,J=7.4Hz,2H),7.14(d,J=8.0Hz,2H),2.37(s,3H). 13 CNMR (101MHz, CDCl3) δ150.5,140.3,139.5,136.6,128.9,128.3,125.3,124.8,120.0,83.5,21.0.

[0156] C11: white solid, 81% yield. 1 H NMR (400MHz, CDCl3) δ7.80 (d, J=7.5Hz, 2H), 7.41–7.35 (m, 2H), 7.35–7.30 (m, 2H), 7.26(td,J=7.2,1.2Hz,2H),7.09(d,J=7.8Hz,2H),7.02–6.92(m,2H),2.32(s,3H). 13 C NMR (101MHz, CDCl3) δ148.1,141.0,138.5,136.4,129.4,129.3,128.9,128.2,127.9,127.3,127.2,125.3,120.1,119.9,21.1. 19F NMR(376MHz, CDCl3)δ-133.07(q,J=11.0,10.1Hz),-162.54(t,J=20.5Hz),-166.64(t,J=20.1Hz).HR-MS(ESI + ) Calculated value C 20 H 15 + m / z[M] + 255.1168; measured value 255.1165.

[0157] C12-S1: white solid, 91% yield. 1 H NMR (400MHz, CDCl3) δ7.90 (d, J=7.6Hz, 2H), 7.59 (dt, J=21.2, 7.6Hz, 6H), 7.45 (t, J=7.5 Hz,2H),7.38(d,J=8.1Hz,2H),3.38(s,1H),2.89(q,J=7.6Hz,2H),1.52(t,J=7.6Hz,3H). 13 C NMR (101MHz, CDCl3) δ150.4,142.7,140.5,139.3,128.7,128.2,127.5,125.3,124.8,119.8,83.4,28.3,15.3.

[0158] C12: white solid, 95% yield. 1 H NMR (400MHz, CDCl3) δ7.80 (dt, J=7.7, 1.0Hz, 2H), 7.37 (tt, J=7.5, 1.0Hz, 2H), 7.34–7.31 (m, 2H), 7.2 9–7.22(m,2H),7.10(d,J=8.2Hz,2H),7.03–6.90(m,2H),2.61(q,J=7.6Hz,2H),1.21(t,J=7.6Hz,3H). 13 C NMR (101MHz, CDCl3) δ148.1,142.7,141.0,138.7,128.2,128.2,127.7,127.3,127.3,125.4,120.1,119.9,28.5,15.5. 19 F NMR(376MHz, CDCl3)δ-132.66,-162.90(t,J=20.5Hz),-166.73.HR-MS(ESI + ) Calculated value C 21 H 17 + m / z[M]+ 269.1325; measured value 269.1321.

[0159] C13-S1: white solid, 96% yield. 1 H NMR (500MHz, CDCl3) δ7.78 (d, J=7.1Hz, 2H), 7.46 (q, J=6.9, 5.9Hz, 4H), 7.31 (ddt, J=35.1, 14.6, 6.4Hz, 5H), 7.16 (t, J=6.3Hz, 1H), 2.38–2.28 (m, 6H). 13 C NMR (101MHz, CDCl3) δ150.6,140.7,139.6,136.4,135.6,129.6,129.0,128.5,126.6,124.8,122.9,120.1,83.6,20.0,19.5.

[0160] C14-S1: white solid, 58% yield. 1 H NMR(400MHz, CDCl3) δ8.21(dd,J=7.7,1.2Hz,2H),7.51(ddd,J=8.4,6.5,2.2Hz,2H),7.38–7.30( m,4H),7.19–7.13(m,1H),7.07(dd,J=8.4,6.7Hz,2H),6.75–6.58(m,4H),2.27(d,J=1.6Hz,1H). 13 C NMR (101MHz, CDCl3) δ146.0,142.5,133.4,131.4,128.8,128.2,127.8,126.8,126.8,124.7,78.9.

[0161] C14: 1 H NMR (400MHz, CDCl3) δ9.04 (s, 2H), 8.67 (dd, J = 8.2, 1.4Hz, 2H), 8.56 (ddd,

[0162] J=8.2,6.8,1.2Hz,2H),8.38(dd,J=8.9,1.2Hz,2H),8.15(ddd,J=8.8,6.9,1.5Hz,2H),7.86–7.79(m,1H),7.78–7.72(m,2H),7.44–7.38(m,2H). 13C NMR (101MHz, CDCl3) δ149.4,147.0,146.8,144.5,141.4,140.6,139.8,138.9,137.5,136.1,135.0,133.3,131.4,130.8,129.5,129.0. 19 F NMR (376MHz, CDCl3) δ-132.9 (m), -162.6 (t, J = 20.6Hz), -166.6 (t, J = 20.0Hz).

[0163] Preparation of C15: 1) Prepare aromatic ketone C15-S1 according to GP3; 2) Prepare polyaryl methyl alcohol C15-S2 from aromatic ketone C15-S1 according to GP4; 3) Prepare tetrafluoroborate ammonium salt C15-S3 from polyaryl methyl alcohol C15-S2 according to GP6; 3) Prepare C15 from tetrafluoroborate ammonium salt C15-S3 according to GP2.

[0164]

[0165] C15-S1: yellow solid, 90% yield. 1 H NMR (400MHz, CDCl3) δ7.89 (d, J = 8.3Hz, 2H), 7.86–7.81 (m, 2H), 7.73–7.67 (m, 2H), 7.63–7.58 (m, 1H), 7.51(dd,J=8.3,6.9Hz,2H),7.35(t,J=7.9Hz,1H),7.01–6.92(m,2H),6.83–6.75(m,1H),3.03(s,6H). 13 C NMR (101MHz, CDCl3) δ196.6,151.1,146.5,141.1,138.0,136.2,132.5,130.8,130.1,129.8,128.4,127.3,115.9,112.5,111.5,40.8.

[0166] C15-S2: yellow viscous liquid, 82% yield. 1 H NMR (400MHz, CDCl3) δ7.56–7.51(m,2H),7.35–7.28(m,13H),6.97(d,J=7.3Hz,2H),6.78(d,J=8.1Hz,1H),3.01(s,6H). 13C NMR (101MHz, CDCl3) δ147.0,145.9,141.9,141.1,141.1,129.6,128.4,128.1,128.1,127.4,127.0,82.1,41.1.

[0167] C15-S3: light brown solid, 87% yield. 1 H NMR (500MHz, DMSO-d6) δ8.16 (s, 1H), 7.71 (dd, J = 8.1, 5.1Hz, 3H), 7.39–7.12 (m, 15H), 3.65 (s, 9H). 13 C NMR (126MHz, DMSO-d6) δ148.0,147.8,147.5,141.9,136.9,130.5,128.4,128.2,127.8,127.7,126.8,126.5,119.1,118.9,80.4,56.4. 19 F NMR(471MHz,DMSO-d6)δ-148.29.HR-MS(ESI + ) Calculated value C 28 H 28 NO + m / z[M] + 394.2165; measured value 394.2162.

[0168] C15: orange solid, 50% yield. 1 H NMR(400MHz,MeOD-d4)δ8.27(t,J=7.5Hz,1H),7.93–7.79(m,5H),7.69(dd,J= 19.8,8.1Hz,4H),7.48(d,J=1.0Hz,2H),7.37–7.28(m,6H),3.70–3.41(m,9H). 13 C NMR (126MHz, MeOD-d4) δ150.4,148.5,145.1,138.5,136.5,132.1,131.3,130. 5,130.4,130.0,129.4,129.3,128.9,128.8,128.3,127.8,127.5,119.5,57.7. 19 F NMR(471MHz,MeOD-d4)δ-133.89(d,J=16.5Hz),-165.79(t,J=19.6Hz),-169.53–-169.81(m).HR-MS(ESI + ) Calculated value C 28 H 28N + m / z[M+H] + 378.2216; measured value 378.2215.

[0169] Preparation of C16: Prepare the ammonium sulfonate salt C16-S3 from polyaryl methyl alcohol C15-S2 according to GP7; prepare the ammonium sulfonate salt C16-S3 according to GP2 to obtain C16.

[0170]

[0171] C16-S3: white solid, 89% yield. 1 H NMR (400MHz, DMSO-d6) δ8.09(d,J=2.4Hz,1H),7.86(dd,J=7.9,4.6Hz,2H),7.77(d,J=8.1Hz,2H),7.70(t,J=8.0Hz,1H),7 .43–7.21(m,9H),7.19–7.14(m,3H),4.05(dt,J=14.5,5.7Hz,2H),3.63(s,6H),2.41(t,J=7.0Hz,2H),1.75–1.54(m,2H). 13 C NMR(101MHz,MeOD-d4)δ146.3,146.2,144.9,138.9,132.2,130.3,130.1,129.9,1 29.2,128.9,128.3,128.0,120.5,120.5,88.1,68.9,55.3,47.3,20.8.HR-MS(ESI + ) Calculated value C 30 H 32 NO4S + m / z[M+H] + 502.2052; measured value 502.2042.

[0172] C16: orange solid, 95% yield. 1 H NMR (400MHz, MeOD-d4) δ7.98(d,J=2.3Hz,1H),7.81(d,J=7.9Hz,1H),7.76(dd,J=8.2,2.6Hz,1H),7.65(dt,J=8.9,2.6Hz,2H),7.53( d,J=8.5Hz,2H),7.42–7.37(m,4H),7.32–7.16(m,7H),4.15–3.98(m,2H),3.64(s,6H),2.74(t,J=6.8Hz,2H),1.89(t,J=8.7Hz,2H). 13C NMR(126MHz,MeOD-d4)δ149.0,147.0,144.8,144.8,143.8,143.7,136.9,135.1,130.8, 129.9,129.6,129.1,128.7,128.0,127.0,126.1,119.0,118.9,67.6,56.3,53.9,19.5. 19 F NMR(376MHz,MeOD-d4)δ-133.97(d,J=16.4Hz),-165.83(t,J=19.7Hz),-169.72(t,J=18.8Hz).HR-MS(ESI + ) Calculated value C 30 H 32 NO3S + m / z[M+2H] + 486.2097; measured value 486.2093.

[0173] Preparation of C17: Prepare the ammonium iodide salt C17-S3 from the polyaryl methyl alcohol C15-S2 according to GP8; prepare the ammonium iodide salt C17-S3 according to GP2 to obtain C17.

[0174]

[0175] C17-S3: white solid, 51% yield. 1 H NMR (400MHz, MeOD) δ8.13 (dd, J=2.8, 1.5Hz, 1H), 7.89 (dt, J=8.2, 2.3Hz, 2H), 7.72 (t, J=8.1Hz,1H),7.70–7.65(m,2H),7.44–7.39(m,2H),7.35–7.24(m,10H),3.74(s,9H). 13 C NMR (101MHz, MeOD) δ149.5,149.2,148.6,144.9,138.9,132.1,130.1,130.1,129.3,128.8,128.2,127.7,119.7,119.6,82.7,57.8.

[0176] C17: pale yellow solid, 45% yield. 1H NMR(500MHz, CDCl3)δ7.80(d,J=7.8Hz,1H),7.78–7.74(m,1H),7.70(t,J=8.0Hz,1H),7.63(dd,J =8.4,3.2Hz,1H),7.53(d,J=8.5Hz,2H),7.47(d,J=8.3Hz,2H),7.36–7.28(m,10H),3.80(s,9H). 13 C NMR (126 MHz, DMSO-d6) δ 148.1, 147.9, 147.5, 146.6, 141.9, 136.9, 136.6, 130.5, 128.4, 127.8, 127.6, 126.8, 126.5, 119.1, 118.9, 80.4, 56.4. No 200 peak. 19 F NMR(471MHz, CDCl3)δ-132.54,-162.33(t,J=20.6Hz),-166.43(t,J=19.5Hz).HR-MS(ESI + ) Calculated value C 28 H 27 N 2+ m / z[M] 2+ 188.7649; measured value 188.6064.

[0177] Preparation of C18: 1) Prepare aromatic ketone C18-S1 according to GP3; 2) Prepare polyaryl methyl alcohol C18-S2 from aromatic ketone C15-S1 according to GP4; 3) Prepare sulfonic acid ammonium salt C18-S3 from polyaryl methyl alcohol C15-S2 according to GP7; 3) Prepare C18 from tetrafluoroborate ammonium salt C18-S3 according to GP2.

[0178]

[0179] C18-S2: white solid, 50% yield. 1 H NMR (400MHz, CDCl3) δ7.54 (d, J = 8.4Hz, 2H), 7.36–7.27 (m, 13H), 6.41 (s, 2H), 2.99 (s, 12H). 13 C NMR (126MHz, CDCl3) δ147.0,145.6,142.7,142.0,128.2,128.1,127.4,127.1,82.1,41.3.

[0180] Preparation of C19: 1) Prepare aromatic ketone C19-S1 according to GP3; 2) Prepare sulfonic acid sodium salt C19-S2 from aromatic ketone C19-S1 according to GP9; 3) Prepare C19 from sulfonic acid sodium salt C19-S2 according to GP2 (Note: KB(C6F5)4 (2.0eq.)).

[0181]

[0182] C19-S1: white solid, 64% yield. 1 H NMR (400MHz, MeOD) δ7.52 (d, J = 8.4Hz, 2H), 7.33–7.20 (m, 13H), 7.08 (dt, J = 7.7, 1.3Hz, 1H), 7.04 (t, J = 2.1Hz, 1H), 6.80–6.71 (m, 1H). 13 C NMR (101MHz, MeOD) δ158.9,148.8,147.9,143.5,141.1,130.8,129.7,129.3,128.7,128.0,127.1,119.3,115.3,114.7,82.8.

[0183] C19-S2: 1 H NMR(500MHz,DMSO-d6)δ7.60(d,J=7.9Hz,2H),7.37–7.13(m,15H),

[0184] 6.90(d,J=8.2Hz,1H),4.12(t,J=6.4Hz,2H),3.57(s,2H),1.77–1.56(m,2H).

[0185] C19: red solid, 60% yield. 1 H NMR(500MHz,MeOD-d4)δ7.55(d,J=7.9Hz,2H),7.48–7.39(m,5H),7.31(t,J=7.6Hz,5H),7.22– 7.09(m,5H),6.89(d,J=8.2Hz,1H),4.15(s,2H),3.01(t,J=7.9Hz,2H),2.26(t,J=8.4Hz,2H). 13C NMR(126MHz,MeOD-d4)δ160.8,150.4,148.5,145.3,144.6,143.4,141.0,140.4,138.5,136.6,130.8 ,130.5,130.3,129.8,129.3,128.8,128.1,127.4,120.5,114.5,114.2,88.2,67.6,61.8,29.2,26.3. 19 FNMR(471MHz,MeOD-d4)δ-133.88(d,J=16.8Hz),-165.79(t,J=19.7Hz),-169.68(t,J=18.8Hz).HR-MS(ESI + ) Calculated value C 28 H 25 O4S + m / z[M] + 457.1468; measured value 457.1466.

[0186] Preparation of C20: 1) preparing aromatic ketone C20-S1 according to GP3; 2) preparing polyaryl methyl alcohol C20-S2 from aromatic ketone C20-S1 according to GP4; 3) preparing sulfonic acid ammonium salt C20-S3 from polyaryl methyl alcohol C20-S2 according to GP7; 4) preparing C20 from sulfonic acid ammonium salt C20-S3 according to GP2.

[0187]

[0188] C20-S1: yellow solid, 95% yield. 1 H NMR (400MHz, CDCl3) δ7.78(d,J=1.8Hz,1H),7.62(d,J=7.4Hz,1H),7.40–7.22(m,10H),7.18(d,J=8.0Hz,1H),2.45(s,1H). 13 C NMR (101MHz, CDCl3) δ150.7,149.4,142.6,141.8,138.4,131.4,129.5,129.4,128.5,127.6,126.5,125.4,125.1,123.5,123.4,120.5,83.4.

[0189] C20-S2: pale yellow solid, 57% yield. 1H NMR(400MHz, CDCl3)δ7.86(d,J=1.6Hz,1H),7.74(d,J=7.5Hz,1H),7.50–7.42(m,3H),7 .42–7.32(m,4H),7.31–7.23(m,5H),7.05–6.93(m,2H),6.84–6.74(m,1H),3.03(s,6H). 13 C NMR (126MHz, CDCl3) δ150.9,149.4,143.6,143.3,142.3,140.2,139.7,129.7,129.3 ,128.7,128.4,128.0,127.4,125.6,125.0,125.0,120.3,119.2,116.2,83.6,41.0.

[0190] C20-S3: light brown solid, 38% yield. 1 H NMR (400MHz, DMSO-d6) δ8.45(d,J=1.7Hz,1H),8.22(s,1H),8.14(d,J=7.6Hz,1H),8.00–7.88(m,2H),7.80–7.70(m,2H),7 .49–7.22(m,8H),7.10(d,J=7.4Hz,1H),4.19–4.10(m,2H),3.69(s,6H),2.55–2.34(m,2H),1.78–1.66(m,2H).HR-MS(ESI + ) Calculated value C 30 H 30 NO4S + m / z[M+H] + 500.1896; measured value 500.1816.

[0191] C20: red solid, 94% yield. 1H NMR (400MHz, DMSO-d6) δ8.44(d,J=1.8Hz,1H),8.21(s,1H),8.13(d,J=7.6Hz,1H) ,7.97(d,J=7.7Hz,1H),7.90(d,J=8.3Hz,1H),7.77(d,J=8.0Hz,1H),7.75–7.69(m ,1H),7.45(t,J=6.8Hz,1H),7.41(d,J=7.9Hz,1H),7.34–7.25(m,5H),7.13–7.05 (m,2H),4.18–4.03(m,2H),3.68(s,6H),2.50(d,J=2.0Hz,2H),1.80–1.59(m,2H). 19 F NMR(376MHz, DMSO-d6)δ-132.40,-161.20(t,J=21.6Hz),-165.84(t,J=20.6Hz). 13 C NMR(101MHz,MeOD-d4)δ150.6,149.7,149.6,148.2,146.1,145.6,143.3,142.7,141.7,139.6,138.7,136.2,132.1,130. 3,129.7,129.2,128.7,128.5,127.9,127.7,126.9,126.3,121.4,120.5,120.2,120.0,70.2,55.4,26.5,20.8.HR-MS(ESI + ) Calculated value C 30 H 30 NO3S + m / z[M+2H] + 484.1941; measured value 484.1942.

[0192] In the following examples, polyethylene terephthalate (PET): η = 0.8907 dL / g; polybutylene terephthalate (PBT): η = 1.1144 dL / g; poly-2,5-furandicarboxylate (PEF): η = 0.8 dL / g.

[0193] General steps

[0194] Hydrolysis: Add 96 mg of polyethylene terephthalate fragments, 0.4-2 mL of water, and triarylmethylonium ion catalyst in a 5 mL sample bottle, seal and heat to 100-120 ° C, and stir to react for several days. After the reaction is completed, filter and wash the solid with water and dichloromethane several times to obtain pure terephthalic acid P1-A. After evaporating and concentrating the water phase, ethylene glycol P2-A can be obtained. After evaporating and concentrating the dichloromethane phase, catalyst C can be recovered and can be reused many times.

[0195]

[0196] Examples 1-6

[0197] The specific conditions and yields of the examples are shown in Table 1.

[0198] Table 1. Different triarylmethylonium ion catalysts used in the general procedure above

[0199]

[0200]

[0201] General steps:

[0202] Acid hydrolysis: Add 96 mg of polyethylene terephthalate fragments, 0.2-0.4 mL of acetic acid, and triarylmethyl onium ion catalyst in a 5 mL sample bottle, seal and heat to 120-150 ° C, and stir for a suitable reaction time. After the reaction is completed, filter and wash the obtained solid with dichloromethane repeatedly several times to obtain pure terephthalic acid P1-A. After the dichloromethane phase is evaporated and concentrated, the polyethylene terephthalate fragments can be added again to perform degradation reaction again. After multiple reactions, ethylene glycol diacetate P3-A can be recovered by distillation.

[0203]

[0204] Examples 7-12

[0205] The specific conditions and yields of the examples are shown in Table 2.

[0206] Table 2. Changes in the amount of substrate and catalyst and reaction time in the above general steps

[0207]

[0208] The main degradation product is terephthalic acid P1-A. 1H NMR (500MHz, DMSO) δ13.26 (s, 2H), 8.04 (s, 4H) and ethylene glycol P2-A, H NMR (500MHz, CDCl3) δ3.76 (s, 4H), 2.28 (br, s) or ethylene glycol diacetate P3-A, 1 H NMR (500MHz, CDCl3) δ4.28 (s, 6H), 2.09 (s, 6H).

[0209] Embodiment 13

[0210] Recovery experiment: 96 mg of polyethylene terephthalate fragments, 0.2 ml of acetic acid (the molar ratio of raw material feeding amount is about 1:6), and 10% C1 (molar ratio with polyester) are added to a 5 ml sample bottle in sequence. The sample bottle is sealed and heated to 150°C, and the reaction is stirred for 8 to 12 hours. After the reaction is completed, it is filtered, and the solid obtained is washed with dichloromethane and dried to obtain 78.0 mg of terephthalic acid P1-A, with an isolated yield of 94%. The obtained filtrate is spin-dried and 96 mg of PET is added again and 0.1 ml of acetic acid is supplemented. The sealed bottle is heated to 150°C, and the reaction is stirred for 24 hours. After filtering, washing the solid, and drying, 78.0 mg of terephthalic acid P1-A is obtained, and the isolated yield is 94%. Repeat the above operation, and the terephthalic acid P1-A is recovered for the third time with an isolated yield of 93%.

[0211] Embodiment 14

[0212]

[0213] In a 5 ml sample bottle, 136 mg of polybutylene terephthalate (fragments, 0.2 ml of glacial acetic acid (the molar ratio of the raw material feeding amount is about 1:6), and 10% C1 (molar ratio to polyester) were added in sequence. The bottle was sealed and heated to 150°C, and the reaction was stirred for 12 hours. After the reaction was completed, the solid was filtered, and the obtained solid was washed with a small amount of ethanol and dried to obtain 69 mg of terephthalic acid P1-A, with an isolated yield of 68%.

[0214] Embodiment 15

[0215]

[0216] In a 5 ml sample bottle, add 92 mg of polyethylene 2,5-furandicarboxylate fragments, 0.2 mL of acetic acid (the raw material feed amount is fixed at 1:6), and 10% C1 (molar ratio to polyester). Seal and heat to 150°C, stir and react for 10 hours. After the reaction is completed, filter, wash the obtained solid with dichloromethane, and dry to obtain 70.1 mg of 2,5-furandicarboxylic acid P1-B, with an isolated yield of 90%. 1 H NMR (500MHz, DMSO) δ13.53 (s, 2H), 7.28 (s, 2H).

Claims

1. Use of a compound as shown in formula II in degrading polyester; in, l, m and p are each independently 0, 1 or 2; It is an anion; Each R 1 , R 2 and R 3 Each is independently halogen, C1-C6 alkyl, C1-C6 alkoxy, C6-C 10 Aryl or one or more R 1-1 Substituted C6-C 10 Aryl; or, for m 1 and p 1 Each is independently 0 or 1; Each R 1-1 Each independently C1-C6 alkoxy or one or more R 1 -1-1 Substituted C1-C6 alkoxy; q is 1, 2, or 3; R a , R b and R c Each is independently a C1-C6 alkyl group; For halide ions or BF4 - ; Each R 1-1-1 Each is independently -SO3H.

2. The use according to claim 1, characterized in that It meets one or more of the following conditions: (1)R 1 , R 2 and R 3 wherein the halogen is independently fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine; (2)R 1 , R 2 and R 3 wherein the C1-C6 alkyl groups are independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl, preferably methyl or ethyl, more preferably methyl; (3)R 1 , R 2 and R 3 wherein the C1-C6 alkoxy groups are independently methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy or tert-butoxy, preferably methoxy; (4)R 1 , R 2 and R 3 In the C6-C 10 The aryl groups are each independently phenyl or naphthyl; preferably phenyl; (5)R 1-1 wherein the C1-C6 alkoxy group is methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy or tert-butoxy, preferably n-propoxy; (6)R a , R b and R c wherein the C1-C6 alkyl groups are independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl, preferably methyl or n-propyl; (7)R 1-1 In the embodiment, the halide ion is a halogen anion, preferably F - , Cl - Br - or I - For example, - ;and (8) It is tetrakis(pentafluorophenyl)borate ion.

3. The use according to claim 1, characterized in that The compound shown in formula II is as follows: l, m and p are each independently 0, 1 or 2; It is an anion; Each R 1 , R 2 and R 3 Each independently is a C1-C6 alkyl group or is replaced by one or more R 1-1 Substituted C6-C 10 Aryl; or for Preferably, it is C1-C6 alkyl or is replaced by one or more R 1-1 Substituted C6-C 10 Aryl; or for m 1 and p 1 Each is independently 0 or 1; Each R 1-1 Each independently or one or more R 1-1-1 Substituted C1-C6 alkoxy; q is 1, 2, or 3; R a and R c Each is independently a C1-C6 alkyl group; Each R 1-1-1 Each is independently -SO3H.

4. The use according to claim 3, characterized in that It satisfies one or both of the following conditions: (1) l is 0, 1 or 2; (2) m is 0, 1 or 2; (3) p is 0, 1 or 2; (4) Each R 1 , R 2 and R 3 Each independently is a C1-C6 alkyl group or is replaced by one or more R 1-1 Substituted C6-C 10 Aryl; or for Preferably, it is C1-C6 alkyl or is replaced by one or more R 1-1 Substituted C6-C 10 Aryl; or for (5)m 1 is 0 or 1; (6)p 1 is 0 or 1; and (7) Each R 1-1 Each independently or one or more R 1-1-1 Substituted C1-C6 alkoxy; Preferably, the compound as shown in Formula II satisfies one or more of the following conditions: (1)R 1 is fluorine, chlorine, bromine, methyl, ethyl, methoxy, phenyl, (2)R 2 is fluorine or methyl; (3)R 3 for (4) for and (5) for 5. The use according to claim 4, characterized in that The compound shown in Formula II is any of the following structures: The anions in compounds C1-C20 are all tetrakis(pentafluorophenyl)borate ions.

6. The use according to any one of claims 1 to 5, characterized in that It is either Option 1 or Option 2: Solution 1 includes the following steps: In water, the polyester is degraded under the action of a compound as shown in Formula II; the polyester comprises repeating units formed by a dicarboxylic acid and a diol; Solution 2 The method comprises the following steps: degrading polyester in carboxylic acid under the action of a compound as shown in Formula II; the polyester comprises repeating units formed by dicarboxylic acid and diol; Among them, l, m, p, R 1 , R 2 , R 3 and The definition as described in any one of claims 1 to 5.

7. The use according to claim 6, characterized in that The structure of the repeating unit is shown in Formula I: Among them, ring A is C6-C 10 An aromatic ring or a 5-6-membered heteroaromatic ring; in the 5-6-membered heteroaromatic ring, the heteroatom is selected from one or more of N, O and S, and the number of the heteroatom is 1 or 2; n is an integer from 1 to 9.

8. The use according to claim 7, characterized in that It meets one or more of the following conditions: (1) In ring A, the C6-C 10 The arylene ring is a phenylene ring or a naphthalene ring; the phenylene ring is preferably (2) In ring A, in the 5-6 membered heteroaromatic ring, the heteroatom is O, and the number of heteroatoms is 1 or 2; the 5-6 membered heteroaromatic ring is preferably a furanyl ring; for example (3) n is an integer of 1-5, preferably 1, 2 or 3; Preferably, ring A is More preferably, the structure of the repeating unit is 9. The use according to claim 8, characterized in that It meets one or more of the following conditions: (1) In scheme 1, the mass volume ratio of the polyester to the water is 30 g / L to 480 g / L; preferably 40 g / L to 300 g / L; for example 48 g / L, 96 g / L or 240 g / L; (2) In scheme 1, the molar ratio of the compound represented by formula II to the polyester is 5% to 50%; preferably 10% to 35%; for example 20% or 28%; (3) In scheme 1, the degradation temperature is 100-150°C, for example, 100°C or 120°C; (4) In scheme 1, the degradation time is 8 to 96 hours, for example, 24 hours, 48 ​​hours or 72 hours; (5) The scheme 1 further comprises the following post-treatment steps: filtering; washing the solid obtained by filtration to obtain a dicarboxylic acid; the washing solvent may be water and / or a halogenated alkane solvent; the halogenated alkane solvent is preferably dichloromethane; (6) In Scheme 2, the carboxylic acid is a C2-C6 carboxylic acid, preferably acetic acid, n-propionic acid or n-butyric acid; more preferably acetic acid; (7) In Scheme 2, the mass volume ratio of the polyester to the carboxylic acid is 60 g / L to 960 g / L; preferably 160 g / L to 720 g / L; for example 240 g / L, 460 g / L, 480 g / L or 680 g / L; (8) In scheme 2, the molar ratio of the compound represented by formula II to the polyester is 1% to 50%; preferably 5% to 40%; more preferably 8% to 30%; for example 10% or 20%; (9) In scheme 2, the degradation temperature is 100 to 180°C, for example, 120°C or 150°C; (10) In scheme 2, the degradation time is 6 to 24 hours, for example 8 hours, 10 hours or 12 hours; (11) The scheme 2 further comprises the following post-treatment steps: filtering; washing the solid obtained by filtration to obtain a dicarboxylic acid; the washing solvent may be a halogenated alkane solvent; the halogenated alkane solvent is preferably dichloromethane; Preferably, in scheme 1, the water, the compound represented by formula II and the polyester are mixed and then degraded; the degradation temperature is preferably 100 to 120° C.; Preferably, in Scheme 2, the carboxylic acid, the compound represented by Formula II and the polyester are mixed and then degraded; the degradation temperature is preferably 120-150°C.

10. The use according to claim 9, characterized in that It satisfies one or both of the following conditions: (1) The scheme 1 further comprises the following post-treatment step: removing the solvent from the filtrate obtained in the filtration step and the washing liquid obtained after washing to obtain a diol; the solvent from the filtrate obtained in the filtration step and the washing liquid obtained after washing is preferably removed by evaporation and concentration; and (2) The scheme 2 further comprises the following post-treatment step: removing the solvent from the filtrate obtained in the filtering step and the washing liquid obtained after washing to obtain diol dicarboxylic acid ester or diol.

11. A compound as shown in formula II: in, R 1 , R 2 , R 3 , The definitions of l, m and p are as described in any one of claims 1 to 5; the compound shown in formula II is not

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