Preparation method of polyurethane with controllable main chain function and sequence

Abstract

The invention belongs to the technical field of preparation of functional high-molecular compounds, and particularly relates to preparation of polyurethane with adjustable main chain function and sequence (unit structure) by a cyclic monomer in various solvents with different polarities under various temperatures and various initiator concentrations in the absence of a catalyst. The ester group, amido bond or ether bond on the main chain structure of the obtained polyurethane can be designed, regulated and controlled according to product requirements, the PDI of the polyurethane can be controlled to be 1.2 or below, which is difficult to realize by other polymerization methods, and the high-precision polyurethane with the structure cannot be obtained by the existing method.

Description

Technical Field

[0001] The invention belongs to the technical field of preparation of functional polymer compounds, and in particular relates to a method for preparing polyurethane with controllable main chain functions and sequences. Background Art

[0002] As the world's sixth largest synthetic material, polyurethane has excellent mechanical properties such as toughness, wear resistance, elasticity, etc. It is widely used in the production of foaming materials, sealing materials, high-performance coatings and adhesives. It is also widely used in the biomedicine field because of its good biocompatibility.

[0003] The synthesis of polyurethane is usually obtained by stepwise polymerization of isocyanate and diol. Isocyanate is highly toxic, so a method for synthesizing non-isocyanate polyurethane has been developed. It can be summarized into two methods: stepwise polymerization and chain polymerization. Stepwise polymerization can achieve the diversity of the main chain functions of the resulting polymer by changing the structure of the monomer, but it is difficult to control the molecular weight and distribution of the resulting polymer; chain polymerization is mainly based on the ring-opening polymerization of small ring molecules containing carbamate bonds. The molecular weight and distribution of the polyurethane prepared by this method are controllable, but due to the limited number of atoms on the small ring monomer, it is difficult to control the changes in the types and sequences of functional groups on the resulting polymer, and the conditions for implementation are relatively harsh: catalysts or high temperature and high pressure conditions are often required. At present, there is no relevant method for synthesizing polyurethanes with controllable main chain functions and sequences, controllable molecular weight, and narrow distribution (PDI <1.1) under mild conditions without catalysis. Summary of the invention

[0004] In order to improve the above technical problems, the present invention first provides a monomer represented by the following formula A or formula B:

[0005]

[0006] In formula A, Ra and Rb are the same or different and are independently selected from H or C 1-6 alkyl;

[0007] Rc is selected from NO2 or C 1-6 Alkyl; q is 1, 2, 3 or 4;

[0008] Rd, Re are the same or different and are independently selected from an ester bond (-COO-), an amide bond (-CONH-), an ether bond (-O-) or an R bond; the R bond is at least one of an ester bond (-COO-), an amide bond (-CONH-), an ether bond (-O-) and at least one C 1-10 A group composed of alkylene groups;

[0009] m is 2, 3, 4 or 5;

[0010] n is 1, 2, 3, 4, 5 or 6;

[0011] s is 1, 2, 3, 4, 5, 6, 7, or 8;

[0012] Provided that the cyclic structure represented by formula A contains 14 or more ring atoms;

[0013]

[0014] In formula B, Rf and Rg are the same or different and are independently selected from H or C 1-6 alkyl;

[0015] Rh is selected from NO2 or C 1-6 Alkyl; p is 1, 2, 3 or 4;

[0016] a is 1, 2, 3, 4 or 5;

[0017] b is 1, 2, 3, 4, 5, 6, 7 or 8;

[0018] c is 0, 1, 2, 3, 4, 5, 6, 7 or 8;

[0019] The condition is that the cyclic structure represented by formula B contains 14 or more ring atoms.

[0020] According to an embodiment of the present invention, Rd, Re are the same or different and are independently selected from an ester bond (-COO-), an amide bond (-CONH-), an ether bond (-O-) or an R bond; the R bond is at least one of an ester bond (-COO-), an amide bond (-CONH-), an ether bond (-O-) and at least one C 1-6 A group composed of connected alkylene groups.

[0021] According to an embodiment of the present invention, in formula A, Rd and Re are the same or different and are independently selected from -COO-, -CONH-, -O-, -C 1-6 Alkylene-COO-, -C 1-6 Alkylene-CONH-, -C 1-6 Alkylene-O-, -C 1-6 Alkylene-COO-C 1-6 Alkylene-, -C 1-6 Alkylene-CONH-C 1-6 Alkylene-, -C 1-6 Alkylene-OC 1-6 Alkylene-, -C 1-6 Alkylene-COO-C 1-6 Alkylene-CONH-, -C 1-6 Alkylene-CONH-C 1-6 Alkylene--O-, -C 1-6 Alkylene-OC 1-6Alkylene -COO-.

[0022] According to an embodiment of the present invention, in formula A, Ra, Rb are the same or different and are independently selected from H or C 1-3 alkyl;

[0023] Rc is selected from NO2 or C 1-6 Alkyl; q is 2 or 3;

[0024] Rd, Re are the same or different and are independently selected from an ester bond or an amide bond;

[0025] m is 2, 3, 4 or 5;

[0026] n is 1, 2, 3, 4, 5 or 6;

[0027] s is 1, 2, 3, 4, 5, 6, 7, or 8;

[0028] The condition is that the cyclic structure represented by formula A contains 14 or more ring atoms.

[0029] In formula B, Rf and Rg are the same or different and are independently selected from H or C 1-3 alkyl;

[0030] Rh is selected from NO2 or C 1-6 Alkyl; p is 2 or 3;

[0031] a is 2, 3, 4 or 5;

[0032] b is 1, 2, 3, 4, 5 or 6;

[0033] c is 1, 2, 3, 4, 5, 6, 7 or 8;

[0034] The condition is that the cyclic structure represented by formula B contains 14 or more ring atoms.

[0035] According to an embodiment of the present invention, in formula A, Ra and Rb are the same and are selected from methyl or ethyl;

[0036] The number of Rc is 2, in which case Rc is selected from NO2 and methyl; or the number of Rc is 3, in which case Rc is selected from 1 NO2 and 2 methyl groups.

[0037] According to the embodiment of the present invention, in Formula A, when Rd, Re are selected from ester bonds (-COO-), amide bonds (-CONH-) or R bonds, it is well known to those skilled in the art that different connection modes of -COO-, -CONH- and R bonds with other parts will lead to different structures of the compounds of Formula A. Therefore, without affecting the stability of the compounds of Formula A, all different stable structures formed by the connection modes of -COO-, -CONH- and R bonds are within the protection scope of the present application.

[0038] According to an embodiment of the present invention, formula A is selected from the structure shown in the following formula A1,

[0039]

[0040] wherein s, m, n, q, Ra, Rb, and Rc have the same definitions as described above.

[0041] According to an embodiment of the present invention, in formula A, Rd and Re are the same and are selected from ester groups;

[0042] According to an embodiment of the present invention, in formula B, Rf and Rg are the same and are selected from methyl or ethyl;

[0043] The number of Rf is 2, in which case Rh is selected from NO2 and methyl; or the number of Rh is 3, in which case Rh is selected from 1 NO2 and 2 methyl groups.

[0044] In one embodiment, the monomer represented by formula A is selected from the following M1:

[0045]

[0046] In one embodiment, the monomer represented by formula B is selected from the following M2:

[0047]

[0048] The present invention also provides a method for preparing the monomer represented by formula A, comprising the following steps:

[0049]

[0050] Compound 2f' first removes the Boc protecting group in an acidic environment, and then undergoes a ring-closing reaction in the presence of an acid-binding agent to obtain monomer A;

[0051] wherein s, m, n, q, Ra, Rb, Rc, Rd, and Re have the same definitions as described above.

[0052] According to an embodiment of the present invention, the monomer represented by formula A is prepared by the following method: Compound 2f' is reacted with TFA by stirring, and after the reaction is completed, TEA is added to react to obtain the monomer represented by formula A.

[0053] According to an embodiment of the present invention, when the monomer represented by formula A is selected from formula A1, compound 2f' is prepared by the following method:

[0054]

[0055] a1) Compound 1a'-1 reacts with compound 1a'-2 to obtain compound 1a';

[0056] a2) Compound 1a' undergoes a reduction reaction to obtain compound 1b';

[0057] a3) Compound 1b' is reacted in the presence of lithium aluminum tetrahydride to obtain compound 1c';

[0058] a4) Compound 1c' reacts with compound TBSCl to obtain compound 1d';

[0059] a5) reacting compound 2a'-1 with boc anhydride to obtain compound 2a';

[0060] a6) Compound 2a′ and compound The reaction yields compound 2b';

[0061] a7) Compound 2b' and compound The reaction gave compound 2c';

[0062] a8) Compound 2c' is first reacted with triphosgene, and then reacted with compound 1d' to obtain compound 2d';

[0063] a9) Compound 2d' is first reacted with Amberlyst 15, and the resulting product is then reacted with PDC to obtain compound 2e';

[0064] a10) Compound 2e' is reacted with pentafluorophenol to obtain compound 2f';

[0065] wherein s, m, n, q, Ra, Rb, and Rc have the same definitions as described above.

[0066] The present invention also provides a method for preparing the monomer represented by formula B, comprising the following steps:

[0067]

[0068] Compound 3f' first removes the Boc protecting group in an acidic environment, and then undergoes a ring-closing reaction in the presence of an acid-binding agent to obtain monomer B;

[0069] wherein a, b, c, p, Rf, Rg and Rh have the same meanings as described above.

[0070] According to an embodiment of the present invention, the monomer represented by formula B is prepared by the following method: Compound 3f' is reacted with TFA by stirring, and after the reaction is completed, TEA is added to react to obtain the monomer represented by formula B.

[0071] According to an embodiment of the present invention, compound 3f' is prepared by the following method:

[0072]

[0073] b1) reacting compound 3a'-1 with TsCl to obtain compound 3a';

[0074] b2) Compound 3a' reacts with sodium azide to obtain compound 3b';

[0075] b3) Compound 3b' is first reacted with triphenylphosphine and then with boc anhydride to obtain compound 3c';

[0076] b4) Compound 3c' is first reacted with triphosgene, and then reacted with compound 2d'-1 to obtain compound 3d';

[0077] b5) Compound 3d' is first reacted with Amberlyst 15, and the resulting product is then reacted with PDC to obtain compound 3e';

[0078] b6) Compound 3e' reacts with pentafluorophenol to obtain compound 3f';

[0079] wherein a, b, c, p, Rf, Rg, and Rh are as defined above;

[0080] The preparation process of 2d'-1 is the same as that of 1d'.

[0081] The present invention also provides the intermediate shown below:

[0082]

[0083]

[0084] wherein s, m, n, a, b, c, p, q, Ra, Rb, Rc, Rf, Rg, and Rh have the same definitions as described above.

[0086] The present invention also provides the use of the monomer compound represented by formula A in preparing the polyurethane represented by formula I below:

[0087]

[0088] Wherein, n1 is an integer of 1-100; s, m, n, Rd, Re, have the same definitions as above.

[0089] The present invention also provides the use of the monomer compound represented by formula B in preparing the polyurethane represented by formula II:

[0090]

[0091] Wherein, n2 is an integer of 1-100; a, b, c have the above definitions.

[0092] The present invention also provides a polyurethane represented by formula I or formula II as described above,

[0093]

[0094] Wherein, n1 is an integer from 1 to 100; s, m, n, Rd, Re, have the above-mentioned definitions;

[0095]

[0096] Wherein, n2 is selected from an integer of 1-100; a, b, c have the above definitions.

[0097] According to an embodiment of the present invention, n1 and n2 are the same or different and are independently selected from integers of 2-80, such as integers of 5-50, 10-30.

[0098] According to an embodiment of the present invention, the PDI of the polyurethane represented by Formula I or Formula II is 1.1 or less, for example, 1.05.

[0099] The present invention also provides a method for preparing a polyurethane represented by formula I or II, comprising the following steps: subjecting the monomer represented by formula A or formula B to a nucleophilic substitution reaction in the presence of an initiator primary amine and / or secondary amine, followed by a ring-opening polymerization reaction to obtain a polyurethane represented by formula I or II;

[0100]

[0101] Among them, n1, n2, s, m, n, a, b, c, p, q, Ra, Rb, Rc, Rd, Re, Rf, Rg, and Rh have the definitions as described above.

[0102] According to an embodiment of the present invention, the initiator is selected from n-hexylamine.

[0103] According to an embodiment of the present invention, the molar feed ratio of the monomer compound represented by formula A, B to the initiator is the same or different, and is independently (1-100):1, such as 25:1, 50:1 or 100:1.

[0104] According to an embodiment of the present invention, the reaction of the monomer represented by formula A or formula B to prepare the polyurethane represented by formula I or II can be carried out in various solvents, such as anisole, toluene, chlorobenzene, DMSO, DMF, etc.

[0105] According to an embodiment of the present invention, the reaction does not require a scavenger and a catalyst, and only requires an initiator to initiate polymerization.

[0106] According to an embodiment of the present invention, the concentration of the polymer monomer represented by formula A or B is 0.1-1.5M, for example 1.5M.

[0107] According to an embodiment of the present invention, the reaction of the monomers represented by formula A or formula B to prepare the polyurethane represented by formula I or II can be carried out at 70-110°C, for example, at 90°C.

[0108] According to an embodiment of the present invention, the reaction time is 1.25-12 hours.

[0109] According to an embodiment of the present invention, after the reaction is completed, the end-capping agent is used to cap the end-portion, followed by precipitation with ether.

[0110] The present invention also provides the use of the polyurethane represented by the above formula I or II as a degradable material.

[0111] Beneficial Effects of the Invention

[0112] The cyclic monomer provided by the present invention can be used in the absence of a catalyst, in a variety of solvents with different polarities, at a variety of temperatures and different initiator and monomer concentrations to prepare polyurethane with adjustable main chain functions and sequences (unit structures). The ester group, amide bond or ether bond on the main chain structure can be designed and regulated according to product requirements, and the PDI of the obtained polyurethane can be controlled below 1.1, which is difficult to achieve with other polymerization methods, and the existing methods cannot obtain the polyurethane with designable structure of the present application. Finally, the by-product lactone compound generated by the polymerization of the present application can be recycled.

[0113] The numerical ranges involved in this application include the endpoints of the range and all numbers between the endpoints. For example, the number "1-100" refers to the endpoints 1 and 100 and all numbers between the endpoints, such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 ... 99. Other numerical ranges have the same definition, such as "C 1-6 Alkyl", "C 1-10 "Alkylene" and "C 1-6 The numerical range of "alkylene" etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0114] Figure 1 is a structural diagram of the monomer M1 prepared in Example 1;

[0115] Figure 2 is a structural diagram of the monomer M2 prepared in Example 1;

[0116] Figure 3 is a schematic diagram of the structure of the high molecular weight polymer I-1 prepared in Example 2;

[0117] Figure 4 is a schematic diagram of the structure of the high molecular weight polymer II-1 prepared in Example 2;

[0118] Figure 5is the NMR spectrum of the monomer M1 prepared in Example 1 (the deuterated reagent used is deuterated dimethyl sulfoxide);

[0119] Figure 6 is the NMR spectrum of the monomer M2 prepared in Example 1 (the deuterated reagent used is deuterated dimethyl sulfoxide);

[0120] Figure 7 This is the NMR spectrum of the high molecular weight polymer I-1 prepared in Example 2 (the deuterated reagent used is deuterated dimethyl sulfoxide, and the conversion rate is calculated);

[0121] Figure 8 This is the in-situ NMR spectrum of the high molecular weight polymer II prepared in Example 2 (the deuterated reagent used is deuterated chloroform);

[0122] Fig. 9 is the GPC chart of the high molecular weight polymer I-1 prepared in Example 2;

[0123] Fig.10 is the GPC chart of the high molecular weight polymer II-1 prepared in Example 2;

[0124] Fig.11 This is the synthesis route of monomer M1 in Example 1.

[0125] Fig.12 This is the synthesis route of monomer M2 in Example 1.

[0126] Fig.13 is the GPC chart of the high molecular weight polymer I-2 prepared in Example 3;

[0127] Fig.14 is the GPC chart of the high molecular weight polymer I-3 prepared in Example 3;

[0128] Fig.15 is the GPC chart of the high molecular weight polymer I-4 prepared in Example 3;

[0129] Fig.16 is the GPC chart of the high molecular weight polymer I-5 prepared in Example 3;

[0130] Fig.17 is the GPC chart of the high molecular weight polymer I-6 prepared in Example 3;

[0131] Fig.18 is the GPC chart of the high molecular weight polymer I-7 prepared in Example 3;

[0132] Fig.19 is the GPC chart of the high molecular weight polymer I-8 prepared in Example 3;

[0133] Fig. 20 is the GPC chart of the high molecular weight polymer I-9 prepared in Example 3;

[0134] Fig.21 is the GPC chart of the high molecular weight polymer I-10 prepared in Example 3;

[0135] Fig. 22 is the GPC chart of the high molecular weight polymer I-11 prepared in Example 3;

[0136] Fig.23 This is the GPC diagram of the polymer before and after degradation in Example 4. DETAILED DESCRIPTION

[0137] The technical scheme of the present invention will be further described in detail below in conjunction with specific embodiments. It should be understood that the following embodiments are only exemplary descriptions and explanations of the present invention and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are included in the scope that the present invention is intended to protect.

[0138] Unless otherwise specified, the raw materials and reagents used in the following examples are commercially available or can be prepared by known methods.

[0139] The test methods in the following examples adopt nuclear magnetic resonance and gel permeation chromatography:

[0140] The liquid NMR spectrometer model was Bruker Avance 400;

[0141] The gel permeation chromatography characterization conditions were: mobile phase DMF, column oven 50°C, flow rate 1 mL / min, and two chromatographic columns AgilentPL Mixed C and Mixed D connected in series.

[0142] Example 1

[0143] 1.1 Preparation route of polymer monomer M1 Fig.11 As shown, the specific steps are:

[0144] 1) Dissolve 3,5-dimethylphenol (40 g) in ether / water (640 mL, v / v=1 / 1), then slowly add sodium nitrate (27.87 g), then slowly add concentrated hydrochloric acid (28 mL), and when the solution turns dark red, the reaction is complete. Then add ethyl acetate for extraction, dry the organic phase, and remove the solvent by rotary evaporation. Purify by column chromatography (petroleum ether) to obtain 3,5-dimethyl-2-nitrophenol (23 g, yield 42%).

[0145] 2) 3,5-dimethyl-2-nitrophenol (23 g) and 3,3-dimethyl acrylate (15.7 g) were dissolved in 100 mL of methanesulfonic acid and stirred at 70°C for 6 h. After cooling, the mixture was diluted with water and extracted with ethyl acetate. The organic phase was dried and the solvent was removed by rotary evaporation. 3,5-dimethyl-2-nitrophenol was recovered by column chromatography with petroleum ether. 石油醚 :V 二氯甲烷 :V 乙酸乙酯 =10:5:1) to obtain the crude product 1a. Recrystallization from dichloromethane and petroleum ether gave purified 1a. The reaction was repeated to obtain a sufficient amount of 1a.

[0146] 3) 1a (10 g) was dissolved in 160 mL of tetrahydrofuran, 4 g of sodium borohydride was slowly added, and the mixture was stirred at 68°C for 12 h. Saturated ammonium chloride solution was slowly added under an ice-water bath to quench the mixture, and ethyl acetate was added for extraction. The organic phase was dried and the solvent was removed by rotary evaporation. Column chromatography (V 石油醚 :V 乙酸乙酯 =5:1) to separate 1b (9.3 g, yield 93%).

[0147] 4) 1b (9.3 g) was dissolved in 140 mL of tetrahydrofuran, and 2 g of lithium aluminum hydride was slowly added. The mixture was stirred at 68°C for 12 h. Saturated ammonium chloride solution was slowly added under an ice-water bath to quench the mixture. Ethyl acetate was added to extract the mixture. The organic phase was dried and the solvent was removed by rotary evaporation. Column chromatography (V 石油醚 :V 乙酸乙酯 =5:1) to separate 1c (7.5 g, yield 80%).

[0148] 5) Dissolve 1c (7.5 g), TBSCl (5 g) and triethylamine (2.5 g) in 60 mL of dichloromethane and react at room temperature for 2 h. Concentrate the solution and perform column chromatography (V 石油醚 :V 乙酸乙酯 =5:1) to separate 1d (10.5 g, yield 97%).

[0149] 6) 6-Amino-1-hexanol (4.45 g) and boc anhydride (9.9 g) were mixed and dissolved in 190 mL of dichloromethane, stirred at room temperature overnight, and the organic phase was washed with dilute hydrochloric acid and saturated sodium bicarbonate in sequence. The organic phase was collected, dried and evaporated to remove the solvent to obtain 2a (8.16 g, yield 99%).

[0150] 7) 2a (7.9 g) and succinic anhydride (5.5 g) were mixed and dissolved in 70 mL of dichloromethane, DMAP (890 mg) was added, and the mixture was stirred at room temperature overnight, and the solvent was removed by rotary evaporation. Column chromatography (V 二氯甲烷 :V 甲醇 =20:1) to give 2b (11.5 g, yield 99%).

[0151] 8) 2b (11.5 g) and 1,3-propylene glycol (13.8 g) were mixed and dissolved in 70 mL of dichloromethane, and DMAP (880 mg) was added. The mixture was stirred at room temperature overnight, and the solvent was removed by rotary evaporation. Column chromatography (V 二氯甲烷 :V 甲醇 =20:1) to give 2c (9.5 g, yield 70%).

[0152] 9) Dissolve triphosgene (3.8 g) in 40 mL tetrahydrofuran, add 2.8 g pyridine dropwise at 0°C, then add 2c (9.5 g) dissolved in 60 mL tetrahydrofuran dropwise to the previous solution, and stir at 0°C for 1 h. Dilute with dichloromethane, wash once with dilute hydrochloric acid, dry the organic phase and spin dry to obtain an intermediate. Dissolve the obtained intermediate in 125 mL dichloromethane, add 1d (10 g) and triethylamine (3.8 g), and stir at room temperature for 1 h. Spin dry and column chromatography (V 石油醚 :V 乙酸乙酯 =5:1) to give 2d (15.5 g, yield 80%).

[0153] 10) 2d (15 g) was dissolved in 200 mL of methanol, and Amberlyst 15 (13 g) was added. The mixture was stirred at room temperature for 1 h. After filtering, the solvent was removed by rotary evaporation to obtain the intermediate. The intermediate, PDC (51 g) and diatomaceous earth (51 g) were mixed and dissolved in 150 mL of DMF, stirred at room temperature overnight, and then filtered through diatomaceous earth, extracted with ether, and hydrochloric acid was added to pH = 4. The organic phase was collected, dried, and the solvent was removed by rotary evaporation. Column chromatography (V 石油醚 :V 乙酸乙酯 =2:3) to give 2e (7.56 g, yield 58%).

[0154] 11) 2e (7.5 g) was mixed with pentafluorophenol (3.1 g) and EDC·HCl (4.3 g) and dissolved in 56 mL THF. DMAP (270 mg) was added and stirred at room temperature overnight. Saturated ammonium chloride solution was then added and extracted with ethyl acetate. The organic phase was collected, dried and evaporated to remove the solvent. Column chromatography (V 石油醚 :V 乙酸乙酯 =3:1) to give 2f (6.5 g, yield 70%).

[0155] 12) Dissolve 2f (6.5 g) and TFA (40 mL) in 40 mL DCM, stir for 15 min, and remove trifluoroacetic acid and dichloromethane by rotary evaporation. Dissolve in 100 mL dichloromethane, and add dropwise to a solution of 10 mL TEA in 500 mL dichloromethane using a syringe pump for 3 h, and remove the solvent by rotary evaporation. Column chromatography (V 石油醚 :V 乙酸乙酯 =8:1) to obtain monomer M1 (3.88 g, yield 90%). Its structure is as follows Figure 1As shown, the NMR spectrum is shown in Figure 5.

[0156] 1.2 Preparation route of polymer monomer M2 Fig.12 As shown, the specific steps are:

[0157] 1) Dissolve hexaethylene glycol (25 g) in 150 mL of dichloromethane, add triethylamine and TsCl (17 g), react overnight at room temperature, spin dry, and column chromatography (V 二氯甲烷 :V 甲醇 =30:1) to give 3a (17.5 g, yield 45%).

[0158] 2) 3a (16.5 g) was dissolved in 75 mL DMF, sodium azide (3.7 g) was added, and the mixture was stirred at 50 °C for 2 h. After drying by spin column chromatography (V 二氯甲烷 :V 甲醇 =30:1) to give 3b (11.6 g, yield 100%).

[0159] 3) 3b (11.6 g) and triphenylphosphine (11.9 g) were dissolved in a mixture of 120 mL tetrahydrofuran and 6 mL water, stirred at room temperature overnight, and then dissolved in 120 mL dichloromethane after being dried by spin drying. 5.7 g triethylamine and 12.4 g boc anhydride were added at 0°C and stirred at room temperature for 2 h. After being dried by spin drying, column chromatography (V 二氯甲烷 :V 甲醇 =30:1) to afford 3c (11.76 g, yield 82%).

[0160] 4) Dissolve triphosgene (3.8 g) in 50 mL tetrahydrofuran, add 2.4 g pyridine dropwise at 0°C, then add 3c (11.7 g) dissolved in 50 mL tetrahydrofuran dropwise to the previous solution, and stir at 0°C for 1 h. Filter and dry to obtain the intermediate. Dissolve the intermediate in 150 mL dichloromethane, add 1d (12.27 g) and triethylamine (3.4 g), and stir at room temperature for 1 h. After drying by column chromatography (V 石油醚 :V 乙酸乙酯 =1:1) to obtain 3d (17.7 g, yield 75%).

[0161] 5) 3d (17.7 g) was dissolved in 230 mL of methanol, and Amberlyst 15 (15 g) was added. The mixture was stirred at room temperature for 1 h. After filtering, the solvent was removed by rotary evaporation to obtain the intermediate. The intermediate, PDC (60 g) and diatomaceous earth (60 g) were mixed and dissolved in 150 mL of DMF, stirred at room temperature overnight, and then filtered through diatomaceous earth, extracted with ether, and hydrochloric acid was added to pH = 4. The organic phase was collected, dried, and the solvent was removed by rotary evaporation. Column chromatography (V 石油醚 :V 乙酸乙酯 =2:3) to give 3e (9 g, yield 58%).

[0162] 6) 3e (9 g), pentafluorophenol (3.7 g) and EDC·HCl (5 g) were mixed and dissolved in 65 mL THF, DMAP (330 mg) was added, and the mixture was stirred at room temperature overnight. Saturated ammonium chloride solution was then added, and the mixture was extracted with ethyl acetate. The organic phase was collected, dried and evaporated to remove the solvent. Column chromatography (V 石油醚 :V 乙酸乙酯 =3:1) to afford 3f (7.88 g, yield 70%).

[0163] 7) 3f (7.88 g) and TFA (48 mL) were dissolved in 48 mL DCM, stirred for 15 min, trifluoroacetic acid and dichloromethane were removed by rotary evaporation, dissolved in 150 mL dichloromethane, and added dropwise to a solution of 15 mL TEA in 1 L dichloromethane using a syringe pump for 3 h, and the solvent was removed by rotary evaporation. Column chromatography (V 二氯甲烷 :V 甲醇 =20:1) to obtain monomer 1 (4.1 g, yield 78.7%). Its structure is as follows Figure 2 As shown, the NMR spectrum is shown in Figure 6.

[0164] Example 2

[0165] 2.1 Preparation of polymer I-1, the specific steps are:

[0166] Add monomer M1 (82.5 mg, 0.15 mmol) to 0.1 mL of anisole, then add n-hexylamine (0.8 mg, 0.006 mmol) to initiate polymerization, incubate in an oil bath at 90°C for 2.75 h, add a capping agent and stir for 6 h. Settle in ether solvent, remove excess monomers and small molecules, and obtain a high molecular weight linear main chain polymer, the structure of which is as follows: Figure 3 As shown, the GPC test results are as follows Fig. 9 As shown. Fig. 9 It can be seen that its relative molecular weight is 26000 and PDI is 1.05. Figure 7 It can be seen that the degree of polymerization is 24.

[0167] 2.2 Preparation of polymer II-1, the specific steps are:

[0168] Add monomer M2 (83.4 mg, 0.15 mmol) to 0.1 mL of anisole, then add n-hexylamine (0.8 mg, 0.006 mmol) to initiate polymerization, incubate in an oil bath at 90°C for 1.25 h, add a capping agent and stir for 6 h. Settle in ether solvent, remove excess monomers and small molecules, and obtain a high molecular weight linear main chain polymer, the structure of which is as follows: Figure 4 The NMR characterization results are shown in Figure 8 The GPC test results are shown in Fig.10 As shown. Fig.10 It can be seen that its relative molecular weight is 22000 and PDI is 1.05. Figure 8 It can be seen that the degree of polymerization is 20.

[0169] Example 3

[0170] Referring to the method of Example 2.1, the solvent anisole was replaced with DMSO, and the molecular weight of polymer I-2 was 27700 and the PDI was 1.05. The GPC test results are as follows Fig.13 shown.

[0171] Referring to the method of Example 2.1, the solvent anisole was replaced with DMF, and the molecular weight of polymer I-3 was 26700 and the PDI was 1.04. The GPC test results are as follows Fig.14 shown.

[0172] Referring to the method of Example 2.1, the solvent anisole was replaced with chlorobenzene, and the molecular weight of polymer I-4 was 26200 and the PDI was 1.03. The GPC test results are as follows Fig.15 shown.

[0173] Referring to the method of Example 2.1, the solvent anisole was replaced by toluene, and the molecular weight of polymer I-5 was 26500 and the PDI was 1.04. The GPC test results are as follows Fig.16 shown.

[0174] Referring to the method of Example 2.1, the reaction temperature was changed to 70°C and the oil bath time was 6h. The molecular weight of polymer I-6 was 27400 and the PDI was 1.05. The GPC test results are as follows Fig.17 shown.

[0175] Referring to the method of Example 2.1, the reaction temperature was replaced with 110°C and the oil bath time was 65 min. The molecular weight of polymer I-7 was 27700 and the PDI was 1.05. The GPC test results are as follows: Fig.18 shown.

[0176] Referring to the method of Example 2.1, the monomer concentration was replaced with 0.2M, the oil bath time was 9h, the molecular weight of polymer I-8 was 26200, and the PDI was 1.06. The GPC test results are as follows Fig.19 shown.

[0177] Referring to the method of Example 2.1, the monomer concentration was replaced with 0.5M, the oil bath time was 5h, the molecular weight of polymer I-9 was 26200, and the PDI was 1.05. The GPC test results are as follows Fig. 20 shown.

[0178] Referring to the method of Example 2.1, the molar ratio of monomer to n-hexylamine was replaced with 50:1, the monomer concentration was 1 M, the oil bath time was 6 h, the molecular weight of polymer I-10 was 50200, and the PDI was 1.03. The GPC test results are as follows Fig.21 shown.

[0179] Referring to the method of Example 2.1, the molar ratio of monomer to n-hexylamine was replaced with 100:1, the monomer concentration was 1M, the oil bath time was 10h, the molecular weight of polymer I-11 was 96500, and the PDI was 1.04. The GPC test results are as follows Fig. 22 shown.

[0180] Example 4

[0181] Degradation by sodium methoxide: 6 mg of polymer I-1 was dissolved in 0.6 mL of tetrahydrofuran, 40 μL of 30% sodium methoxide was added, and the mixture was monitored at room temperature for 1 h. 0.25 mL of 0.25 M dilute hydrochloric acid solution was added, and the mixture was extracted with dichloromethane three times and dried. The GPC test results were as follows: Fig.23 As shown in the GPC test results, it can be seen that the polymer prepared in this application can be used as a degradable material.

[0182] The above is an explanation of the embodiments of the present invention. However, the present invention is not limited to the above embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A compound represented by formula A or formula B: In formula A, Ra and Rb are the same or different and are independently selected from H or C 1-6 alkyl; Rc is selected from NO2 or C 1-6 Alkyl; q is 1, 2, 3 or 4; Rd, Re are the same or different and are independently selected from an ester bond (-COO-), an amide bond (-CONH-), an ether bond (-O-) or an R bond; the R bond is at least one of an ester bond (-COO-), an amide bond (-CONH-), an ether bond (-O-) and at least one C 1-10 A group composed of alkylene groups; m is 2, 3, 4 or 5; n is 1, 2, 3, 4, 5 or 6; s is 1, 2, 3, 4, 5, 6, 7, or 8; Provided that the cyclic structure represented by formula A contains 14 or more ring atoms; In formula B, Rf and Rg are the same or different and are independently selected from H or C 1-6 alkyl; Rh is selected from NO2 or C 1-6 Alkyl; p is 1, 2, 3 or 4; a is 1, 2, 3, 4 or 5; b is 1, 2, 3, 4, 5, 6, 7 or 8; c is 0, 1, 2, 3, 4, 5, 6, 7 or 8; The condition is that the cyclic structure represented by formula B contains 14 or more ring atoms.

2. The compound according to claim 1, characterized in that In formula A, Rd and Re are the same or different and are independently selected from an ester bond (-COO-), an amide bond (-CONH-), an ether bond (-O-) or an R bond; the R bond is at least one of an ester bond (-COO-), an amide bond (-CONH-), an ether bond (-O-) and at least one C 1-6 A group composed of alkylene groups; Preferably, in formula A, Rd and Re are the same or different and are independently selected from -COO-, -CONH-, -O-, -C 1-6 Alkylene-COO-, -C 1-6 Alkylene-CONH-, -C 1-6 Alkylene-O-, -C 1-6 Alkylene-COO-C 1-6 Alkylene-, -C 1-6 Alkylene-CONH-C 1-6 Alkylene-, -C 1-6 Alkylene-OC 1-6 Alkylene-, -C 1-6 Alkylene-COO-C 1-6 Alkylene-CONH-, -C 1-6 Alkylene-CONH-C 1-6 Alkylene--O-, -C 1-6 Alkylene-OC 1-6 Alkylene -COO-.

3. The compound according to claim 1, characterized in that In formula A, Ra and Rb are the same or different and are independently selected from H or C 1-3 alkyl; Rc is selected from NO2 or C 1-6 Alkyl; q is 2 or 3; Rd, Re are the same or different and are independently selected from an ester bond or an amide bond; m is 2, 3, 4 or 5; n is 1, 2, 3, 4, 5 or 6; s is 1, 2, 3, 4, 5, 6, 7, or 8; The condition is that the ring structure contains 14 or more ring atoms. Preferably, in formula B, Rf and Rg are the same or different and are independently selected from H or C 1-3 alkyl; Rh is selected from NO2 or C 1-6 Alkyl; p is 2 or 3; a is 2, 3, 4 or 5; b is 1, 2, 3, 4, 5 or 6; c is 1, 2, 3, 4, 5, 6, 7 or 8; The condition is that the ring structure contains 14 or more ring atoms. Preferably, in formula A, Ra and Rb are the same and are selected from methyl or ethyl; The number of Rc is 2, in which case Rc is selected from NO2 and methyl; or the number of Rc is 3, in which case Rc is selected from 1 NO2 and 2 methyl groups. Preferably, in Formula A, when Rd, Re are selected from ester bonds (-COO-), amide bonds (-CONH-) or R bonds, it is well known to those skilled in the art that different connection modes of -COO-, -CONH- and R bonds with other parts will result in different structures of the compounds of Formula A. Therefore, without affecting the stability of the compounds of Formula A, all different stable structures formed by the connection modes of -COO-, -CONH- and R bonds are within the protection scope of the present application.

4. The compound according to any one of claims 1 to 3, characterized in that Formula A is selected from the structure shown in the following formula A1, Wherein, s, m, n, q, Ra, Rb and Rc have the definitions as described in any one of claims 1 to 3. Preferably, the monomer represented by formula A is selected from the following M1: Preferably, the monomer represented by formula B is selected from the following M2:

5. A method for preparing the compound according to any one of claims 1 to 4, characterized in that: The preparation method of the monomer represented by formula A comprises the following steps: Compound 2f' first removes the Boc protecting group in an acidic environment, and then undergoes a ring-closing reaction in the presence of an acid-binding agent to obtain monomer A; Wherein, s, m, n, q, Ra, Rb, Rc, Rd and Re have the definitions as described in any one of claims 1 to 4. Preferably, the method for preparing the monomer represented by formula B comprises the following steps: Compound 3f' first removes the Boc protecting group in an acidic environment, and then undergoes a ring-closing reaction in the presence of an acid-binding agent to obtain monomer B; Wherein, a, b, c, p, Rf, Rg and Rh have the definitions as described in any one of claims 1 to 4.

6. Intermediates as shown below: in, s, m, n, a, b, c, p, q, Ra, Rb, Rc, Rf, Rg and Rh have the definitions as described in any one of claims 1 to 4.

7. Use of the compound according to any one of claims 1 to 4 in the preparation of polyurethane, characterized in that: The monomer compound shown in formula A is used to prepare the polyurethane shown in the following Ⅰ: Wherein, n1 is an integer from 1 to 100; s, m, n, Rd, Re, have the definitions as described in any one of claims 1 to 4; The monomer compound shown in formula B is used to prepare the polyurethane shown in formula II: Wherein, n2 is an integer of 1-100; a, b, c have the definitions as described in any one of claims 1-4.

8. A polyurethane of formula I or II, in, n1 is an integer from 1 to 100; s, m, n, Rd, Re have the meanings as defined in any one of claims 1 to 4; Wherein, n2 is selected from an integer of 1-100; a, b, c have the definitions as described in any one of claims 1-4.

9. The method for preparing the polyurethane according to claim 8, characterized in that: The method comprises the following steps: a monomer represented by formula A or formula B undergoes a nucleophilic substitution reaction in the presence of a primary amine and / or a secondary amine as an initiator, followed by a ring-opening polymerization reaction to obtain a polyurethane represented by formula I or II; Among them, n1, n2, s, m, n, a, b, c, p, q, Ra, Rb, Rc, Rd, Re, Rf, Rg, and Rh have the definitions as described in claim 8.

10. Use of the polyurethane according to claim 8 as a degradable material.

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