Main chain sequence controllable poly(epsilon-caprolactone-epsilon-caprolactam) and preparation method and application thereof

Abstract

The application discloses a kind of main chain sequence controllable poly (epsilon-caprolactone-epsilon-caprolactam) and its preparation method and application, the poly (epsilon-caprolactone-epsilon-caprolactam) is prepared by the monomer compound of formula A or the monomer compound of formula B reaction preparation;Poly (epsilon-caprolactone-epsilon-caprolactam) shown in formula II is prepared by reaction.The monomer compound of formula A or the monomer compound of formula B provided in the application can prepare poly (epsilon-caprolactone-epsilon-caprolactam) in the presence of lower temperature, weak base, the number average molecular weight of poly (epsilon-caprolactone-epsilon-caprolactam) is 20,000 or more, its main chain structure is ordered arrangement, and PDI is controlled at 1.2 or less, significantly better than the preparation method in the prior art, and the application can prepare high-precision poly (epsilon-caprolactone-epsilon-caprolactam).

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of functional polymer compound preparation, and particularly relates to a poly(epsilon-caprolactone-epsilon-caprolactam) with controllable main chain sequence and a preparation method and application thereof. BACKGROUND

[0002] As important polymer materials (Macromolecules 2014, 47, 2471-2478), polyester amides have the characteristics of excellent mechanical properties and environmental friendliness, and these materials have better biodegradability and biocompatible degradation products, thus attracting the interest and extensive attention of the modern engineering plastics industry.

[0003] As a common polyester amide, the synthesis of poly(epsilon-caprolactone-epsilon-caprolactam) is currently limited to the following methods: (a) anionic copolymerization of different initiators, (b) interfacial copolymerization; (c) anionic ring-opening copolymerization. High molecular weight random polymers can be prepared by using the above three methods, but due to the inherent problems of monomer sequence synthesis in the polymerization method, the content of ester bonds and amide bonds in the polymer cannot be controlled. Researchers (Polym. Chem. 2020, 11, 1211-1219) used synthetic sequence monomers to obtain different content (ester bonds and amide bonds) of main chains by solution polycondensation, and also studied the thermal stability, phase change behavior, crystallinity, wettability and thermal responsiveness of the polymer, but the actual sequence is still unclear, and the dispersity of the polymer (PDI>1.4) cannot be controlled. The polymer obtained by traditional anionic ring-opening copolymerization also has unclear sequence and uncontrollable dispersity, and has the problem of harsh reaction conditions (high temperature and high pressure). There is currently no method to synthesize poly(epsilon-caprolactone-epsilon-caprolactam) with controllable main chain sequence. SUMMARY

[0004] To improve the above technical problems, the present application provides a monomer compound of the following formula A or a monomer compound of the following formula B:

[0005]

[0006]

[0007] wherein p is an integer from 0 to 3; when p is 2 or 3, each R1 is the same or different, and is independently selected from H, C 1-12 alkyl, C 1-12 alkoxy, halogen, cyano, nitro, amino or formyl.

[0008] According to an embodiment of the present application, p is an integer from 0 to 3, preferably p is 1, 2 or 3; more preferably p is 1 or 2, and most preferably p is 1.

[0009] According to embodiments of the present application, when p is 2 or 3, each R1is the same or different, independently selected from H, C 1-6 alkyl, C 1-6 alkoxy, halogen, cyano, nitro, amino, or formyl.

[0010] According to embodiments of the present application, each R1is the same or different, independently selected from H, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, or n-hexyl, preferably t-butyl.

[0011] Preferably, the monomer compound of Formula A has the following structure:

[0012]

[0013] Preferably, the monomer compound of Formula B has the following structure:

[0014]

[0015] The present application also provides a method for preparing the monomer compound of Formula A or Formula B as described above, comprising the following steps:

[0016] (K1) reacting a compound of Formula C with pentafluorophenyl carbonate in a solvent to prepare an intermediate 6;

[0017]

[0018] (K2) reacting the intermediate 6, trifluoroacetic acid (TFA), and a basic catalyst in a solvent to prepare the monomer compound of Formula A;

[0019] Alternatively, (P1) reacting a compound of Formula D with pentafluorophenyl carbonate in a solvent to prepare an intermediate 10;

[0020]

[0021] (P2) reacting the intermediate 10, trifluoroacetic acid (TFA), and a basic catalyst in a solvent to prepare the monomer compound of Formula B.

[0022] According to embodiments of the present application, the solvent is at least one of dichloromethane (DCM), tetrahydrofuran (THF), chloroform (CHCl3), acetonitrile, or a combination of two or more thereof.

[0023] According to an embodiment of the present application, the basic catalyst is at least one of triethylamine, diisopropylethylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), or a combination of two or more thereof.

[0024] According to an embodiment of the present application, the method for preparing the compound of Formula C comprises the following steps:

[0025] (1) reacting the compound of Formula E with tert-butyldimethylsilyl chloride (TBSCl) to prepare an intermediate 1;

[0026]

[0027] (2) reacting 1-amino hexanoic acid, di-tert-butyl dicarbonate (boc anhydride), and triethylamine to prepare an intermediate 2;

[0028] (3) reacting the intermediate 2 with hexanediol to prepare an intermediate 3;

[0029] (4) reacting the intermediate 3 with the intermediate 1 to prepare an intermediate 4;

[0030] (5) reacting the intermediate 4 with an ion exchange resin (Amberlyst 15) to prepare the compound of Formula C, i.e., an intermediate 5.

[0031] According to an embodiment of the present application, the method for preparing the compound of Formula D comprises the following steps:

[0032] (S1) reacting the above intermediate 3 with hexanediol to prepare an intermediate 7;

[0033] (S2) reacting the intermediate 7 with the intermediate 1 to prepare an intermediate 8;

[0034] (S3) reacting the intermediate 8 with an ion exchange resin (Amberlyst 15) to prepare the compound of Formula D, i.e., an intermediate 9.

[0035] The present application also provides a poly(ε-caprolactone-ε-caprolactam) of Formula I or Formula II, wherein the poly(ε-caprolactone-ε-caprolactam) of Formula I is prepared by the reaction of the above monomer compound of Formula A; and the poly(ε-caprolactone-ε-caprolactam) of Formula II is prepared by the reaction of the above monomer compound of Formula B;

[0036]

[0037] wherein n is the same or different and is independently selected from a number of 1-100;

[0038] Preferably, n is the same or different and independently of one another selected from a number from 15 to 50; exemplarily 15, 20, 25, 20, 30, 35, 40, 45 or 50.

[0039] According to an embodiment of the present application, the poly(ε-caprolactone-ε-caprolactam) of Formula I or Formula II has a number average molecular weight of 20000 or more, such as from 22000 to 200000.

[0040] The present application also provides a method for preparing the poly(ε-caprolactone-ε-caprolactam) of Formula I or Formula II, the method comprising the following steps:

[0041] reacting the monomer compound of Formula A with an initiator to prepare the poly(ε-caprolactone-ε-caprolactam) of Formula I;

[0042] or, reacting the monomer compound of Formula B with an initiator to prepare the poly(ε-caprolactone-ε-caprolactam) of Formula II.

[0043] According to an embodiment of the present application, the initiator is at least one of n-hexylamine, n-propylamine, phenylpropylamine or a combination of two or more thereof.

[0044] Exemplarily, when in the monomer compound of Formula A or Formula B, p is 1 and R1 is tert-butyl, the preparation of the poly(ε-caprolactone-ε-caprolactam) of Formula I or Formula II is as follows:

[0045]

[0046] or,

[0047]

[0048] According to an embodiment of the present application, the molar ratio of the monomer compound of Formula A or Formula B to the initiator is from 30 to 60:1, such as 30:1, 40:1, 45:1, 50:1, 55:1 or 60:1.

[0049] According to an embodiment of the present application, the method is carried out in a polar solvent, such as DMSO and / or DMF.

[0050] According to an embodiment of the present application, the method is carried out in the presence of a trapping agent, such as N-methylaniline.

[0051] According to an embodiment of the present application, the method is further carried out under catalysis of an organic amine, such as at least one of triethylamine, diisopropylethylamine, DBU, TBD or a combination of two or more thereof.

[0052] According to an embodiment of the present application, the molar ratio of the monomer compound of formula A or formula B, the organic amine, the trapping agent, the initiator is (30-60):(3-6):(75-120):1, for example 30:3:75:1 or 30:3:120:1.

[0053] According to an embodiment of the present application, the method is carried out at 30-70℃, for example 30℃, 40℃, 50℃, 60℃, 70℃.

[0054] According to an embodiment of the present application, the reaction is carried out for 1-72h.

[0055] According to an embodiment of the present application, the method further comprises a post-treatment step after the reaction: the reaction product is settled in diethyl ether, and the unreacted monomer and initiator are removed.

[0056] The present application also provides the use of the monomer compound of formula A, the monomer compound of formula B, the poly(ε-caprolactone-ε-caprolactam) of formula I or the poly(ε-caprolactone-ε-caprolactam) of formula II in the preparation of plastics, fiber materials.

[0057] The present application has the following advantages:

[0058] The monomer compound of formula A or the monomer compound of formula B provided by the present application can be used to prepare poly(ε-caprolactone-ε-caprolactam) at a lower temperature in the presence of a weak base (for example TEA), the number average molecular weight of the poly(ε-caprolactone-ε-caprolactam) is more than 20,000, the main chain structure is orderly arranged (i.e. the ester groups and amide bonds on the main chain are arranged in the order of -ABBABBABB- or -ABABABAB-), and the PDI is controlled to be less than 1.2, which is significantly better than the preparation method in the prior art, and the present application can prepare high-precision poly(ε-caprolactone-ε-caprolactam).

[0059] Definitions of terms

[0060] The numerical range referred to in the present application means that all the numbers including the end points and the numbers between the end points are included, for example, the numbers of "1-100" mean the end points 1 and 100 and all the numbers between the end points, for example 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13……99. Other numerical ranges have the same definition, for example 1-6, etc.

[0061] The term "C 1-12 "alkyl" means straight-chain and branched-chain alkyl groups having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms, "C 1-6"Alkyl" denotes straight and branched chain alkyl groups having 1, 2, 3, 4, 5, or 6 carbon atoms. The alkyl group is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, t-butyl, isopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, neopentyl, 1,1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl, or 1,2-dimethylbutyl, and the like or isomers thereof.

[0062] The term "C 1-12 "Alkoxy" refers to a group of the formula -O-alkyl, wherein alkyl is as defined above. 1-12 "Alkoxy" refers to a group of the formula -O-alkyl, wherein alkyl is as defined above. BRIEF DESCRIPTION OF DRAWINGS

[0063] Figure 1 NMR spectrum of monomer A prepared in Example 1 (deuterated reagent used was deuterated dimethyl sulfoxide);

[0064] Figure 2 NMR spectrum of monomer B prepared in Example 1 (deuterated reagent used was deuterated dimethyl sulfoxide);

[0065] Figure 3 In situ NMR spectrum of polymer I prepared in Example 2 (deuterated reagent used was deuterated dimethyl sulfoxide, conversion calculated, polymer insoluble after settling);

[0066] Figure 4 NMR spectrum of polymer II prepared in Example 2 (deuterated reagent used was deuterated dimethyl sulfoxide);

[0067] Figure 5 GPC plot of polymer I prepared in Example 2;

[0068] Figure 6 GPC plot of polymer II prepared in Example 2;

[0069] Figure 7 DSC plot of polymers I and II prepared in Example 2.

[0070] Figure 8 TGA plot of polymers I and II prepared in Example 2. DETAILED DESCRIPTION

[0071] The technical solutions of the present application will be further described in detail below in combination with specific examples. It should be understood that the following examples are only illustratively described and explained, and should not be interpreted as limiting the scope of protection of the present application. Any technology realized based on the above description of the present application is covered within the scope of protection intended by the present application.

[0072] Unless otherwise specified, the raw materials and reagents used in the following examples are commercially available or can be prepared by known methods.

[0073] The instruments or conditions for the tests performed in Examples 1-2 are as follows:

[0074] Liquid nuclear magnetic resonance spectrometer model: Bruker Avance 400;

[0075] DSC differential scanning calorimeter model: DSC Q2000;

[0076] TGA thermal gravimetric analyzer model: PerkinElmer Pyris 1TGA;

[0077] Gel permeation chromatography (GPC) characterization conditions: mobile phase DMF, column oven 50℃, flow rate 1 ml / min, Agilent PL Mixed C, Mixed D two in series.

[0078] Example 1

[0079] 1.1 The preparation route of the monomer compound of formula A (p is 1, R1 is 2-tert-butyl), i.e. monomer A, is shown below,

[0080]

[0081] The specific steps are as follows:

[0082] 1) 2-(tert-butyl)-4-(hydroxymethyl)-6-nitrophenol (6 g) and TBSCl (4.4 g) were mixed with imidazole (2 g) in 30 ml of DMF, stirred at room temperature for 1 h, then diluted with ether, washed with water to remove DMF, and the organic phase was dried over anhydrous magnesium sulfate, and the solvent was removed by rotary evaporation. The residue was purified by column chromatography (V 石油醚 :V 乙酸乙酯 = 20:1) to obtain intermediate 1 (9 g, yield 95%).

[0083] 2) 1-amino hexanoic acid (5 g) and boc anhydride (16.6 g) were mixed in 380 ml of methanol, triethylamine (8 ml) was added, stirred at 60℃ for 1 h, then adjusted to pH = 4 with dilute hydrochloric acid, collected the organic phase, dried, and the solvent was removed by rotary evaporation; obtained intermediate 2 (8.6 g, yield 98%).

[0084] 3) Intermediate 2 (9 g) from the previous step and hexanediol (18 g), 1-ethyl-(3- dimethylaminopropyl)carbodiimide hydrochloride (EDC hydrochloride) (15 g) were mixed in 150 ml of THF, 4-dimethylaminopyridine (DMAP) (950 mg) was added and stirred at room temperature overnight. Then, a saturated solution of ammonium chloride was added and the organic phase was collected and dried over anhydrous magnesium sulfate. The solvent was removed by rotary evaporation. The residue was purified by column chromatography (V 石油醚 :V 乙酸乙酯 = 2:1) to give intermediate 3 (9.5 g, 74% yield).

[0085] 4) Intermediate 3 (8 g) from the previous step and pyridinium dichromate (PDC) (32 g) were mixed in 120 ml of DMF and stirred at room temperature overnight. Then, the mixture was filtered over celite and the organic phase was collected and dried. The solvent was removed by rotary evaporation. The residue was purified by column chromatography (V 石油醚 :V 乙酸乙酯 = 1:1) to give a crude product. The crude product was mixed with intermediate 1 (6.4 g), EDC hydrochloride (6 g) in 80 ml of THF, DMAP (380 mg) was added and stirred at room temperature overnight. Then, a saturated solution of ammonium chloride was added and the organic phase was collected and dried over anhydrous magnesium sulfate. The solvent was removed by rotary evaporation. The residue was purified by column chromatography (V 石油醚 :V 乙酸乙酯 = 2:1) to give intermediate 4 (12 g, 73% yield).

[0086] 5) Intermediate 4 (12 g) from the previous step and ion exchange resin Amberlyst 15 (16 g) were mixed in 170 ml of methanol and stirred at room temperature for 2 h. The solvent was removed by rotary evaporation after filtration. The residue was purified by column chromatography (V 石油醚 :V 乙酸乙酯 = 1:1) to give intermediate 5 (9 g, 93% yield).

[0087] 6) Intermediate 5 (5 g) from the previous step and pentafluorophenyl carbonate (7.1 g), TEA (2.5 ml) were mixed in 90 ml of DCM and stirred at room temperature for 1 h. The solvent was removed by rotary evaporation. The residue was purified by column chromatography (V 石油醚 :V 乙酸乙酯 = 3:1) to give intermediate 6 (6.7 g, 97% yield).

[0088] 7) Intermediate 6 (6.7 g) from the previous step was dissolved in 30 ml of DCM and trifluoroacetic acid (TFA) (30 ml) was added. The mixture was stirred for 15 minutes and the trifluoroacetic acid and DCM were removed by rotary evaporation. The residue was dissolved in 100 ml of DCM and added dropwise to a solution of 10 ml of TEA in 500 ml of DCM using a syringe pump over 3 hours. The solvent was removed by rotary evaporation. The residue was purified by column chromatography (V 石油醚 :V 乙酸乙酯 = 1 : 1) to give monomer A (3 g, 71% yield), which had the NMR spectrum shown in Figure 1. Figure 1

[0089] 1.2 Preparation of monomer compound of formula B, i.e. monomer B, is shown in the following scheme,

[0090]

[0091] The specific steps are as follows:

[0092] 1) Intermediate 3 (11 g) from the previous step was mixed with PDC (44 g) and dissolved in 150 ml of DMF. The mixture was stirred at room temperature overnight, filtered through celite, extracted with ether, the organic phase was collected and dried over anhydrous magnesium sulfate, and the solvent was removed by rotary evaporation. The residue was purified by column chromatography (V 石油醚 :V 乙酸乙酯 = 1 : 1) to give a crude product, which was mixed with hexanediol (15 g) and EDC hydrochloride (9.7 g) and dissolved in 120 ml of THF. DMAP (622 mg) was added and the mixture was stirred at room temperature overnight. Saturated ammonium chloride solution was then added, the mixture was extracted with ethyl acetate, the organic phase was collected and dried over anhydrous magnesium sulfate, and the solvent was removed by rotary evaporation. The residue was purified by column chromatography (V 石油醚 :V 乙酸乙酯 = 2: 1) to give intermediate 7 (8 g, 54% yield).

[0093] 2) Intermediate 7 (7.3 g) from the previous step was mixed with PDC (37 g) and dissolved in 90 ml of DMF. The mixture was stirred at room temperature overnight, filtered through celite, extracted with ether, the organic phase was collected and dried, and the solvent was removed by rotary evaporation. The residue was purified by column chromatography (V 石油醚 :V 乙酸乙酯 = 1 : 1) to give a crude product, which was mixed with intermediate 1 (5.6 g) and EDC hydrochloride (5.3 g) and dissolved in 60 ml of THF. DMAP (330 mg) was added and the mixture was stirred at room temperature overnight. Saturated ammonium chloride solution was then added, the mixture was extracted with ethyl acetate, the organic phase was collected and dried over anhydrous magnesium sulfate, and the solvent was removed by rotary evaporation. The residue was purified by column chromatography (V 石油醚 :V 乙酸乙酯 = 2: 1) to give intermediate 8 (8.3 g, 65% yield).

[0094] ​3) Mix intermediate 8 (8.7g) and Amberlyst 15 (7.2g) in 60ml methanol, stir at room temperature for 2h, filter and evaporate the solvent. Purify the residue by column chromatography (V 石油醚 :V 乙酸乙酯 =1:1) to obtain intermediate 9 (6.2g, yield 83%).

[0095] 4) Mix intermediate 9 (5.5g) and pentafluorophenyl carbonate (6.5g), TEA (2.3ml) in 80ml DCM, stir at room temperature for 1h, evaporate the solvent. Purify the residue by column chromatography (V 石油醚 :V 乙酸乙酯 =3:1) to obtain intermediate 10 (7g, yield 97%).

[0096] 7) Mix intermediate 10 (7g), TFA (30ml) in 30ml DCM, stir for 15min, evaporate TFA and DCM, dissolve in 100ml DCM, add 3h by injection pump to 10ml TEA in 500ml DCM, evaporate the solvent. Purify the residue by column chromatography (V 石油醚 :V 乙酸乙酯 =1:1) to obtain monomer B (4.2g, yield 89%). The NMR spectrum of monomer B is shown in Figure 2 .

[0097] Example 2

[0098] 2.1 Preparation of poly(ε-caprolactone-ε-caprolactam) represented by formula I, i.e. polymer I, in detail:

[0099] Add monomer A (287mg, 0.6mmol), TEA (6.1mg, 0.06mmol), N-methylaniline (161mg, 1.5mmol) and n-hexylamine (2mg, 0.02mmol) in 1ml DMSO to initiate polymerization, react in 50°C oil bath for 72h, place the residue in ether to settle, remove unreacted monomer and small molecules to obtain polymer I, whose structural formula is shown in formula I. The GPC test result is shown in Figure 5 . It is known from Figure 5 that the number average molecular weight is 24000 and PDI is 1.07. Figure 3 The in-situ NMR spectrum of polymer I is shown in Figure 3 , which shows that the polymerization degree is 19.

[0100] 2.2 Preparation of poly(ε-caprolactone-ε-caprolactam) represented by formula II, i.e. polymer II, in detail:

[0101] Monomer B (710 mg, 0.6 mmol), TEA (12.2 mg, 0.06 mmol), N-methylaniline (257 mg, 2.4 mmol), and n-hexylamine (2 mg, 0.02 mmol) were added to 1 ml of DMSO to initiate polymerization. The reaction was carried out in an oil bath at 50 °C for 72 h. The residue was then placed in diethyl ether to precipitate and remove unreacted monomers and small molecules, yielding polymer II. The NMR characterization results are as follows: Figure 4 As shown; GPC test results are as follows Figure 6 As shown, by Figure 6 It can be seen that its number-average molecular weight is 33,000 and its PDI is 1.07. Figure 4 The NMR spectrum of polymer II is shown below. Figure 4 The degree of polymerization is 22.

[0102] DSC and TGA spectra of polymers I and II were obtained through detection. Figure 7 DSC plots for polymers I and II; Figure 8 TGA diagrams of polymers I and II.

[0103] The embodiments of the present invention have been described above by way of example. However, the scope of protection of the present invention is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc., made by those skilled in the art within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for producing a monomer compound of the following formula A or a monomer compound of the following formula B, characterized by, The method comprises the following steps: (K1) reacting a compound shown in formula C with pentafluorophenyl carbonate in a solvent to prepare intermediate 6; (K2) reacting intermediate 6, trifluoroacetic acid (TFA) and a basic catalyst in a solvent to prepare a monomer compound of formula A; Or, (P1) reacting a compound shown in formula D with pentafluorophenyl carbonate in a solvent to prepare intermediate 10; (P2) reacting intermediate 10, trifluoroacetic acid (TFA) and a basic catalyst in a solvent to prepare a monomer compound of formula B; The preparation method of the compound shown in formula C comprises the following steps: (1) reacting a compound shown in formula E with tert-butyldimethylsilyl chloride (TBSCl) to prepare intermediate 1; (2) reacting 1-amino hexanoic acid, di-tert-butyl dicarbonate and triethylamine to prepare intermediate 2; (3) reacting intermediate 2 with hexanediol to prepare intermediate 3; (4) reacting intermediate 3 with intermediate 1 to prepare intermediate 4; (5) reacting intermediate 4 with ion exchange resin to prepare the compound shown in formula C, i.e. intermediate 5; The preparation method of the compound shown in formula D comprises the following steps: (S1) reacting the above intermediate 3 with hexanediol to prepare intermediate 7; (S2) reacting intermediate 7 with intermediate 1 to prepare intermediate 8; (S3) reacting intermediate 8 with ion exchange resin to prepare the compound shown in formula D, i.e. intermediate 9; 2. The method of claim 1, wherein, The solvent is at least one of dichloromethane, tetrahydrofuran, chloroform and acetonitrile or a combination of two or more thereof.

3. The method of claim 1, wherein, The basic catalyst is at least one of triethylamine, diisopropylethylamine, DBU and TBD or a combination of two or more thereof.

4. Poly(ε-caprolactone-ε-caprolactam) represented by Formula I or Formula II, characterized in that, The poly(ε-caprolactone-ε-caprolactam) shown in formula I is prepared by reacting the monomer compound of formula A according to claim 1; and the poly(ε-caprolactone-ε-caprolactam) shown in formula II is prepared by reacting the monomer compound of formula B according to claim 1. Wherein, n is the same or different and independently selected from a number of 1-100.

5. The poly(ε-caprolactone-ε-caprolactam) according to claim 4, characterized in that, n is the same or different and independently selected from a number of 15-50.

6. The poly(ε-caprolactone-ε-caprolactam) according to claim 4, characterized in that, The number average molecular weight of the poly(ε-caprolactone-ε-caprolactam) of formula I or formula II is 20000 or more.

7. The process for the preparation of poly(ε-caprolactone-ε-caprolactam) according to claim 5 or 6, characterized in that, The method comprises the following steps: Reacting the monomer compound of formula A with an initiator to prepare the poly(ε-caprolactone-ε-caprolactam) shown in formula I; Or, reacting the monomer compound of formula B with an initiator to prepare the poly(ε-caprolactone-ε-caprolactam) shown in formula II.

8. The method of claim 7, wherein, The initiator is at least one of n-hexylamine, n-propylamine and phenylpropylamine or a combination of two or more thereof.

9. Use of the monomer compound of formula A or the monomer compound of formula B prepared by the method according to claim 1, and the poly(ε-caprolactone-ε-caprolactam) according to claim 5 or 6 in preparing plastics and fiber materials.

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