A compound imitating spider silk structure and its preparation method and application

Abstract

The present invention discloses a compound imitating the structure of natural spider silk, and a preparation method and application thereof. The compound molecule is similar to natural spider silk, and contains conformations such as spiral, folded and random coils. Polydiol reacts with diisocyanate to generate a flexible chain, and the molecular conformation is a random coil; while the polypeptide PBLG presents a spiral and folded conformation, which is used to improve the strength of the material. The preparation method of the material provided by the present invention has a simple process, a high yield, and good application prospects and scientific significance.

Description

Technical Field

[0001] The invention belongs to the field of organic materials, and in particular relates to a compound with a spider silk-like structure and a preparation method and application thereof. Background Art

[0002] Materials play a vital role in promoting the process of social development. In modern times, the successful synthesis and industrial application of lightweight polymer materials have greatly facilitated people's lives, and with the preparation of more and more new materials, polymer materials have also shown great advantages in replacing metal materials. However, the strength and toughness of materials are generally a pair of contradictions, and the preparation of materials with both high strength and high modulus has always been a great challenge. Materials with high tensile strength (greater than 40MPa) and Young's modulus (greater than 1.0GPa) are usually brittle due to their extremely low elongation at break (less than 10% in most cases), while materials with high toughness show relatively low tensile strength and Young's modulus.

[0003] In nature, spider silk is a material that is recognized to have both high strength and high modulus. The mechanical properties of current artificial materials are basically not comparable to spider silk. According to the literature (Nature Reviews, 2018, 3, 8000.), the tensile strengths of artificial steel and Kevlar fiber are 1.6 GPa and 3.6 GPa respectively, and the strength of spider silk can reach 1.7 GPa; but spider silk can also maintain a high enough toughness (artificial steel toughness: 6 MJ·m -3 ; Kevlar fiber toughness: 60MJ·m -3 ; Spider silk toughness: 350MJ·m -3 ). The extremely high toughness of spider silk comes from its low density, high tensile strength and good ductility, so spider silk usually has a high energy absorption capacity. Studies have found that spider silk is mainly composed of proteins, and the molecular weight of each monomer is usually 250-400kDa. The repeated arrangement of proteins gives spider silk β-helix, β-fold and random coil conformations. Among them, proteins with β-fold conformation are orderly arranged through hydrogen bonds to form crystalline regions, which improves the strength of spider silk; proteins with β-helix and random coil conformations provide the elasticity of spider silk.

[0004] Polypeptides are composed of amino acids or derivatives, similar to protein structures. Polypeptides have stable structures, good biocompatibility and biodegradability, and can be degraded into small molecules in the body and metabolized by the body. The realization of controlled ring-opening polymerization of N-carboxyl cyclic anhydride (NCA) has made the synthesis of polypeptides a research hotspot, greatly expanding the application field of polypeptide materials. Among them, poly (L-benzyl glutamate) (PBLG) is a polypeptide structure with multiple conformations obtained by the polymerization of glutamic acid and benzyl alcohol. The type of conformation is related to the molecular weight, and it has the characteristics of easy processing, easy functionalization and biocompatibility.

[0005] Scientists have been committed to preparing artificial silk comparable to spider silk through chemical synthesis methods, and have made great progress. For example, Tsuchiya's team prepared a multi-block peptide with both lamellar crystals and helical structures through a two-step chemical synthesis method. Although this structure is similar to natural spider silk in conformation, it has a lower molecular weight and poorer mechanical properties. Therefore, it is still a great challenge to prepare a polypeptide material that is easy to process and has good mechanical properties. Summary of the invention

[0006] In order to improve the above technical problems, the present invention provides a compound represented by formula (I):

[0007]

[0008] Wherein, p is an integer from 1 to 10;

[0009] x is 5 to 20; y is 2 to 10; m is 2 to 40; n is 10 to 100;

[0010] R is selected from H, unsubstituted or optionally substituted with one, two or more R a Substituted C 1-8 Alkyl; each R a The same or different, independently selected from unsubstituted or optionally substituted by one, two or more R a1 Substituted OH, NH2, COOH, C(O)NH2, C 6-14 aryl, 5-14 membered heteroaryl, SH; each R a1 are the same or different and are independently selected from H, unsubstituted or optionally substituted with one, two or more R a2 Substituted OH, NH2, COOH, SH, C 1-8 Alkyl; each R a2 are the same or different and are independently selected from H, OH, NH2, COOH, SH, unsubstituted or optionally substituted with one, two or more R a3 Substituted C 1-8 Alkyl, C 6-14Aryl, 5-14 membered heteroaryl; each R a3 The same or different, independently selected from H, OH, NH2, COOH, SH, C 1-8 alkyl;

[0011] A is selected from unsubstituted, or optionally substituted with one, two or more R b Substituted C 1-8 Alkylene, 3-10 membered cycloalkylene-C 1-8 Alkyl, C 6-14 Arylene, -A1-CH2-A2-; each R b The same or different, independently selected from C 1-8 Alkyl, 3-10 membered cycloalkyl, C 6-14 Aryl, COOC 1-8 Alkyl; A1 or A2 are the same or different and are independently selected from 3-10 membered cycloalkylene, C 6-14 Arylene.

[0012] According to an embodiment of the present invention, p is an integer of 2-8; x is 6-18; y is 2-8; m is 10-30; n is 20-50;

[0013] R is selected from H, unsubstituted or optionally substituted with one, two or more R a Substituted C 1-6 Alkyl; each R a The same or different, independently selected from unsubstituted or optionally substituted by one, two or more R a1 Substituted COOH, C 6-14 Aryl; each R a1 are identical or different, independently selected from OH, unsubstituted or optionally substituted with one, two or more R a2 Substituted C 1-8 Alkyl; each R a2 The same or different, independently selected from C 6-14 Aryl;

[0014] A is selected from unsubstituted, or optionally substituted with one, two or more R b Substituted C 1-6 Alkylene, 3-8 membered cycloalkylene-C 1-6 Alkyl, C 6-8 Arylene, -A1-CH2-A2-; each R b The same or different, independently selected from C 1-6 Alkyl, 3-8 membered cycloalkyl, C 6-8 Aryl, COOC 1-3 Alkyl; A1 or A2 are the same or different and are independently selected from 3-8 membered cycloalkylene, C 6-8 Arylene.

[0015] According to an embodiment of the present invention, p is 5;

[0016] x is 8, 9, 10, 11 or 12; y is 2, 3, 4, 5 or 6; m is 18, 19, 20, 21, 22, 23 or 24; n is 24, 25, 26, 27, 28, 29 or 30;

[0017] R is selected from one, two or more R a Substituted methyl, ethyl; each R a The same or different, independently selected from Ph(CH2)OC(O)-, phenyl, hydroxyphenyl;

[0018] A is selected from

[0019] According to an embodiment of the present invention, the compound of formula (I) has a structure shown in formula (I-1):

[0020]

[0021] wherein p, x, y, m, n, R, and A have the definitions given above.

[0022] The present invention provides a method for preparing a compound represented by formula (I), comprising the following steps:

[0023]

[0024] (a) Compound 1 reacts with triphosgene to obtain compound 2;

[0025] (b) Compound 2 reacts with compound 3 (initiator) to obtain compound 4;

[0026] (c) Compound 5 reacts with compound 6 (chain extender) to obtain compound 7;

[0027] (d) Compound 7 reacts with compound 4 to obtain a compound represented by formula (I);

[0028] wherein p, x, y, m, n, R, and A have the definitions given above.

[0029] According to an embodiment of the present invention, in step (a), the reaction can be carried out in an organic solvent, and the organic solvent can be at least one of ester, amide, aromatic and other solvents;

[0030] According to an embodiment of the present invention, in step (a), the reaction temperature is 50-120°C, for example, 65°C to 90°C, exemplified by 70°C and 75°C; the reaction time is 1-12h, for example, 2 to 8h;

[0031] According to an embodiment of the present invention, in step (a), the reaction is carried out in an inert gas, and the inert gas may be nitrogen or argon;

[0032] According to an embodiment of the present invention, in step (a), the product obtained by the reaction can be further precipitated and purified in an ether solvent, and the ether solvent can be petroleum ether;

[0033] Preferably, the compound 1 in step (a) is selected from at least one of glutamic acid, L-glutamic acid, R-glutamic acid, aspartic acid, L-aspartic acid, R-aspartic acid, tyrosine or phenylalanine.

[0034] According to an embodiment of the present invention, in step (b), the reaction can be carried out in an organic solvent, and the organic solvent can be at least one of esters, amides, ethers, aromatic solvents, etc.; ethers, such as ethyl propyl ether, n-butyl ether, anisole, phenethyl ether, cyclohexyl methyl ether, dimethyl ether, ethyl ether, dimethyl ethylene glycol, biphenyl ether, propyl ether, isopropyl ether, isobutyl ether, isoamyl ether, ethylene glycol dimethyl ether, isopropyl ethyl ether, methyl tert-butyl ether, tetrahydrofuran, methyltetrahydrofuran, dioxane, dichlorodiethyl ether, and polyethers of ethylene oxide and / or propylene oxide; aromatic hydrocarbons, such as fluorobenzene, chlorobenzene or dichlorobenzene, benzene, toluene, chlorobenzene, bromobenzene, xylene; esters such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate and dimethyl carbonate, dibutyl carbonate or ethylene carbonate; amides, such as dimethylformamide, dimethylacetamide, N,N-dimethylformamide dimethyl acetal.

[0035] According to an embodiment of the present invention, in step (b), the compound 3 may be an organic amine compound containing two or more amino groups; for example, at least one of ethylenediamine, propylenediamine, butylenediamine, pentanediamine, and hexamethylenediamine;

[0036] According to an embodiment of the present invention, in step (b), the reaction temperature is 0 to 30°C, for example, 5 to 25°C, exemplified by 20°C and 25°C; the reaction time is 5 to 100h, for example, 24 to 72h, exemplified by 72h;

[0037] According to an embodiment of the present invention, in step (b), the molecular weight of the compound 4 may be 200-5000, for example, 500-2000;

[0038] According to an embodiment of the present invention, in step (b), an inert gas may be introduced into the reaction during the reaction to remove the generated carbon dioxide gas and promote the reaction to proceed in the forward direction. The inert gas may be nitrogen or argon.

[0039] According to an embodiment of the present invention, in step (c), the molar ratio of compound 6 to compound 5 in the reaction is 1.01:1 to 5:1, for example, 1.1:1 to 2:1, exemplified by 1.2:1, 1.3:1, 1.5:1, 3.1:2, 1.6:1, 1.8:1;

[0040] According to an embodiment of the present invention, in step (c), a catalyst may be added to the reaction, and the catalyst is an organic tin catalyst, for example, at least one selected from trimethyltin, trimethyltin chloride, triethyltin, butyltin dilaurate, triethyltin chloride, triethyltin bromide, triethyltin iodide, triethyltin hydroxide, triethyltin sulfate, bistriethyltin sulfate, tributyltin chloride, triphenyltin chloride, triphenyltin acetate, tetraethyltin, tetrabutyltin, tetraphenyltin, triethyltin bromide (Umisan), and triethyltin sulfate, preferably butyltin, and more preferably butyltin dilaurate.

[0041] According to an embodiment of the present invention, in step (c), the reaction temperature is 30 to 100° C., for example, 60 to 90° C., and exemplarily 80° C.; the reaction time is 1 to 5 hours, for example, 2 to 4 hours, and exemplarily 3 hours;

[0042] Preferably, the compound 6 in step (c) is selected from isocyanate compounds, for example, it can be at least one of toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), hexamethylene diisocyanate (HDI), and lysine diisocyanate (LDI).

[0043] According to an embodiment of the present invention, in step (d), compound 4 can be directly added to the reaction system of step (c) to react and obtain a compound represented by formula (I);

[0044] According to an embodiment of the present invention, in step (d), the molar ratio of compound 4 to compound 5 in step (c) may be 1:1.2-1:3, for example, 1:1.5-1:2.5, exemplarily 1:2;

[0045] According to an embodiment of the present invention, in step (d), the reaction temperature is 30-100°C, for example, 60-90°C, and exemplarily 80°C; the reaction time is 2-24h, for example, 8-15h, and exemplarily 12h.

[0046] Preferably, in step (a), when the compound 1 is selected from glutamic acid, L-glutamic acid, R-glutamic acid, aspartic acid, L-aspartic acid, and R-aspartic acid, the method further comprises step (a'): a step in which compound 1 reacts with benzyl alcohol to obtain compound 1', and compound 1' is further reacted with step (a) to obtain compound 2; the compound 1' is benzyl glutamate or benzyl aspartate;

[0047] According to an embodiment of the present invention, in step (a'), the molar ratio of compound 1 to benzyl alcohol may be 1:0.8 to 1:8, for example, 1:1 to 1:5, exemplified by 1:2, 1:3, 1:4;

[0048] According to an embodiment of the present invention, in step (a'), the reaction temperature is 30-100°C, such as 50-75°C, exemplified by 70°C or 75°C.

[0049] The present invention also provides an intermediate compound 4 having the structure shown below:

[0050]

[0051] wherein R has the definition given above.

[0052] The present invention also provides the use of the intermediate compound 4 in the preparation of the compound of formula (I).

[0053] The present invention also provides application of the compound as a bionic material, for example, as a spider silk imitating material.

[0054] Beneficial Effects

[0055] The compound imitating the structure of natural spider silk disclosed in the present invention is similar to natural spider silk, and contains conformations such as spiral, folded and random coils, wherein polydiol reacts with diisocyanate to generate a flexible chain, and the molecular conformation is a random coil; and the polypeptide PBLG is presented in a spiral and folded conformation, which is used to improve the strength of the material. The compound provided by the present invention has good mechanical strength and excellent toughness performance, and can be used as a spider silk imitating material. The preparation method thereof has a simple process flow and a high yield. BRIEF DESCRIPTION OF THE DRAWINGS

[0056] Figure 1 For Example 1 1 H NMR characterization results, where a is the spectrum of the PBLG triblock copolymer initiated by pentamethylenediamine, and b is the spectrum of the final obtained spider silk-like structure.

[0057] Definition and explanation of terms

[0058] Unless otherwise specified, the definitions of groups and terms recorded in the specification and claims of this application, including their definitions as examples, exemplary definitions, preferred definitions, definitions recorded in tables, definitions of specific compounds in examples, etc., can be arbitrarily combined and combined with each other. The definitions of groups and compound structures after such combinations and combinations should be understood to be within the scope of the specification and / or claims of this application.

[0059] Unless otherwise specified, the numerical ranges recorded in this specification and claims are equivalent to recording at least each specific integer value therein. For example, the numerical range "1-100" is equivalent to recording each integer value in the numerical range "1-10", namely 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, and each integer value in the numerical range "11-100", namely 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 ... 95, 96, 97, 98, 99, 100. In addition, when certain numerical ranges are defined as "numbers", it should be understood that the two endpoints of the range, each integer in the range, and each decimal in the range are recorded. For example, “a number from 0 to 10” should be understood as not only recording each integer of 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10, but also recording at least the sum of each of these integers and 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 respectively.

[0060] It should be understood that herein, when describing one, two or more, "more" should refer to an integer greater than 2, for example, greater than or equal to 3, for example 3, 4, 5, 6, 7, 8, 9 or 10.

[0061] The term "halogen" refers to fluorine, chlorine, bromine and iodine.

[0062] The term "C 1-8 "Alkyl" means a straight-chain or branched saturated hydrocarbon radical having 1, 2, 3, 4, 5, 6, 7 or 8 carbon atoms. 1-6 The term "alkyl" refers to straight-chain and branched 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, tert-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, or the like or isomers thereof.

[0063] Terminology The term "C3-10 "Cycloalkyl" is understood to mean a saturated monovalent monocyclic, bicyclic (eg bridged, spiro) hydrocarbon ring or tricyclic alkane having 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms. 3-10 The cycloalkyl group may be a monocyclic hydrocarbon group such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl or cyclodecyl, or a bicyclic hydrocarbon group such as borneol, indolyl, hexahydroindolyl, tetrahydronaphthyl, decahydronaphthyl, bicyclo[2.1.1]hexyl, bicyclo[2.2.1]heptyl, bicyclo[2.2.1]heptenyl, 6,6-dimethylbicyclo[3.1.1]heptyl, 2,6,6-trimethylbicyclo[3.1.1]heptyl, bicyclo[2.2.2]octyl, 2,7-diazaspiro[3,5]nonanyl, 2,6-diazaspiro[3,4]octanyl, or a tricyclic hydrocarbon group such as adamantyl.

[0064] The term "C 6-14 The term "aryl" is understood to mean preferably an aromatic or partially aromatic monocyclic, bicyclic or tricyclic hydrocarbon ring having 6 to 14 carbon atoms, for example 6, 7, 8, 9, 10, 11, 12, 13 or 14 carbon atoms. For example, a ring having 6 carbon atoms ("C6 aryl"), such as phenyl or biphenyl, or a ring having 9 carbon atoms ("C9 aryl"), such as indanyl or indenyl, or a ring having 10 carbon atoms ("C 10 aryl), such as tetrahydronaphthyl, dihydronaphthyl or naphthyl, or a ring having 13 carbon atoms ("C 13 aryl), such as fluorenyl, or a ring having 14 carbon atoms ("C 14 aryl”), such as anthracenyl. When the C 6-14 When the aryl group is substituted, it may be monosubstituted or polysubstituted. Also, there is no limitation on the substitution position, for example, it may be substituted at the ortho position, para position or meta position.

[0065] The term "5-14 membered heteroaryl" is understood to include monovalent monocyclic, bicyclic or tricyclic aromatic ring systems having 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14 ring atoms, in particular 5 or 6 or 9 or 10 carbon atoms, and containing 1 to 5, preferably 1 to 3 heteroatoms independently selected from N, O and S. And, in each case, it may be benzo-fused. "Heteroaryl" also refers to a group in which a heteroaromatic ring is fused to one or more aromatic, alicyclic or heterocyclic rings, wherein the radical or point of attachment is on the heteroaromatic ring. When the heteroaryl is connected to other groups to form the compounds of the present invention, it may be connected to other groups by carbon atoms on the heteroaryl ring or by heteroatoms on the heteroaryl ring. When the heteroaryl is substituted, it may be monosubstituted or polysubstituted. Furthermore, there is no limitation on the substitution site, for example, a hydrogen atom connected to a carbon atom on a heteroaryl ring may be substituted, or a hydrogen atom connected to a heteroatom on a heteroaryl ring may be substituted.

[0066] In particular, the heteroaryl group is selected from thienyl, furanyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl, pyrazolyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, thiadiazolyl, thia-4H-pyrazolyl and the like and benzo derivatives thereof, such as benzofuranyl, benzothienyl, benzoxazolyl, benzisoxazolyl, benzimidazolyl, benzotriazolyl, indazolyl, indolyl, isoindolyl and the like; or pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl and the like and benzo derivatives thereof, such as quinolyl, quinazolinyl, isoquinolyl and the like; or azinyl, indolizinyl, purinyl and the like and benzo derivatives thereof; or cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, naphthyridinyl, pteridinyl, carbazolyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl and the like.

[0067] The term "spirocyclic" refers to a ring system in which two rings share one ring-forming atom.

[0068] The term "fused ring" refers to a ring system in which two rings share two ring atoms.

[0069] The term "bridged ring" refers to a ring system in which two rings share three or more ring atoms.

[0070] The term "alkylene" means a group in which two bonds are substituted; for example, "alkylene" means an "alkyl" in which two bonds are substituted, "cycloalkylene" means a "cycloalkyl" in which two bonds are substituted, "arylene" means an "aryl" in which two bonds are substituted, and "heteroarylene" means a "heteroaryl" in which two bonds are substituted.

[0071] Unless otherwise specified, heterocyclic groups, heteroaryls or heteroarylene groups include all possible isomeric forms thereof, such as positional isomers thereof. Thus, for some illustrative non-limiting examples, forms substituted or bonded to other groups at 1, 2 or more positions in the 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11-, 12-positions, etc. (if present) may include pyridin-2-yl, pyridin-2-ylene, pyridin-3-yl, pyridin-3-ylene, pyridin-4-ylene and pyridin-4-ylene; thienyl or thienylene groups include thien-2-yl, thien-2-ylene, thien-3-ylene and thien-3-ylene; pyrazol-1-yl, pyrazol-3-yl, pyrazol-4-yl, pyrazol-5-yl.

[0072] The term "number average molecular weight" refers to the sum of the product of the fractions of molecules of different molecular weights in a polymer and their corresponding molecular weights. DETAILED DESCRIPTION

[0073] 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.

[0074] Unless otherwise specified, the raw materials and reagents used in the following examples are commercially available or can be prepared by known methods.

[0075] Unless otherwise specified, the feed ratios described in the present invention are all molar ratios of the reactants.

[0076] Example 1

[0077] (1) Synthesis of γ-benzyl-L-glutamate five-membered cyclic anhydride (BLG-NCA)

[0078] Weigh 200g L-glutamic acid and 150mL benzyl alcohol respectively, mix them in 60wt% concentrated sulfuric acid, react at 70℃ for 3h, cool the obtained liquid and adjust the pH to neutral, let it stand and filter to obtain a powdered product. The product is recrystallized in hot water (~80℃) and vacuum dried to obtain BLG. Weigh 20g BLG, add ethyl acetate, add 1.5 times the molar equivalent of triphosgene solid when heated to 70℃, and continue to react for 5h. Then adjust the solution pH to neutral, filter and add the filtrate to petroleum ether for precipitation, and vacuum dry to obtain BLG-NCA monomer. The synthesis route of BLG-NCA is shown below.

[0079]

[0080] (2) Synthesis of PBLG block copolymers

[0081] Weigh 5g of dried BLG-NCA, add 50mL DMF and mix well, add 0.149mL of pentamethylenediamine, and react at room temperature for 3 days. The polymer solution is precipitated in anhydrous ethanol and dried to obtain a powdery product with a yield of 89%. The number average molecular weight of the obtained triblock polymer product is 4000-5000. The synthesis steps are as follows. Figure 1 Where a is a triblock copolymer 1 H NMR spectrum. It can be seen from the figure that the characteristic peak of the benzyl group on the PBLG main chain is at δ = 5.1 ppm, and the characteristic peak of hydrogen on the benzene ring is near δ = 7.3 ppm.

[0082]

[0083] (3) Synthesis of spider silk-like polymer PMB

[0084] Weigh 6 g of PTMEG and dry it in vacuum at 80°C for 3 h. Then add 1.02 mL of IPDI and 0.06 g of catalyst (butyltin dilaurate). Stir the reaction at 80°C for 3 h. Then add the DMF solution (5 mL, concentration of 1.0 g / mL) of the PBLG triblock polymer obtained in step (2) and continue the reaction at 80°C for 12 h to obtain a polymer yield of 92%. The molar ratio of PTMEG, PBLG and IPDI is PTMEG:PBLG:IPDI=2:1:3.1. The reaction path is shown below, and the number average molecular weight of the final polymer is 220,000, where n=27, m=21, x=10, and y=4.

[0085] Figure 1 b is the final polymer 1 H NMR spectrum. Compared with the PBLG triblock copolymer spectrum a, the characteristic peaks of polyether alcohol are added in spectrum b, and their positions are around 1.5 ppm and 3.8 ppm.

[0086]

[0087] Example 2

[0088] (1) Synthesis of γ-benzyl-L-aspartic acid ester five-membered cyclic anhydride (ALG-NCA)

[0089] Weigh 210g L-aspartic acid and 155mL benzyl alcohol respectively, mix them in 60wt% concentrated sulfuric acid, react at 75℃ for 3h, adjust the pH of the obtained liquid to neutral after cooling, let it stand and filter to obtain a powdery substance. The product is recrystallized in hot water (~85℃) and vacuum dried to obtain ALG. Weigh 20g ALG, add ethyl acetate, add 1.5 times the molar equivalent of triphosgene solid when heated to 70℃, and continue to react for 5h. Then adjust the pH of the solution to neutral, filter and add the filtrate to petroleum ether for precipitation, and vacuum dry to obtain ALG-NCA monomer.

[0090] (2) Synthesis of PALG block copolymers

[0091] Weigh 5g of dried ALG-NCA, add 50mL of anhydrous DMF and mix well, then add 0.149mL of pentamethylenediamine and react at room temperature for 3 days. The polymer solution is precipitated in anhydrous ethanol and dried to obtain a powdery product with a yield of 87%. The molecular weight of the obtained PALG triblock polymer product is 4000-5000.

[0092] (3) Synthesis of spider silk-like polymer PMA

[0093] Weigh 6 g of PTMEG and dry it in vacuum at 80°C for 3 h. Then add 1.02 mL of IPDI and 0.06 g of catalyst (butyltin dilaurate). Stir and react at 80°C for 3 h. Then add the DMF solution (5 mL, concentration of 0.92 g / mL) of the PALG triblock polymer obtained in step (2) and continue the reaction at 80°C for 12 h. The yield of the obtained polymer is 90%. The number average molecular weight of the final polymer is 230,000, where n=27, m=22, x=10, and y=4.

[0094] Example 3

[0095] (1) Synthesis of γ-benzyl-L-glutamate five-membered cyclic anhydride (BLG-NCA)

[0096] Weigh 200g L-glutamic acid and 150mL benzyl alcohol respectively, mix them in 60wt% concentrated sulfuric acid, react at 70℃ for 3h, cool the obtained liquid and adjust the pH to neutral, let it stand and filter to obtain a powdered product. The product is recrystallized in hot water (~80℃) and vacuum dried to obtain BLG. Weigh 20g BLG, add ethyl acetate, add 1.5 times the molar equivalent of triphosgene solid when heated to 70℃, and continue to react for 5h. Then adjust the solution pH to neutral, filter and add the filtrate to petroleum ether for precipitation, and vacuum dry to obtain BLG-NCA monomer.

[0097] (2) Synthesis of PBLG block copolymers

[0098] Weigh 5g of dried BLG-NCA, add 50mL DMF and mix well, add 0.149mL of pentamethylenediamine, and react at room temperature for 3 days. The polymer solution is precipitated in anhydrous ethanol and dried to obtain a powdery product with a yield of 89%. The number average molecular weight of the obtained PBLG triblock polymer product is 4000-5000.

[0099] (3) Synthesis of spider silk-like polymer PMB

[0100] Weigh 5 g of PTMEG and dry it in vacuum at 80°C for 3 h. Then add 1.02 mL of IPDI and 0.06 g of catalyst (butyltin dilaurate). Stir and react at 80°C for 3 h. Then add the DMF solution (5 mL, concentration of 1.0 g / mL) of the PBLG triblock polymer obtained in step (2) and continue the reaction at 80°C for 12 h. The yield of the obtained polymer is 89%. The number average molecular weight of the final polymer is 240,000, where n=27, m=23, x=10, and y=4.

[0101] Example 4

[0102] (1) Synthesis of γ-benzyl-L-glutamate five-membered cyclic anhydride (BLG-NCA)

[0103] Weigh 200g L-glutamic acid and 150mL benzyl alcohol respectively, mix them in 60wt% concentrated sulfuric acid, react at 70℃ for 3h, adjust the pH of the obtained liquid to neutral after cooling, and filter to obtain a powdery substance after standing. The product is recrystallized in hot water (~80℃) and vacuum dried to obtain BLG. Weigh 20g BLG, add ethyl acetate, add 1.5 times the molar equivalent of triphosgene solid when heated to 70℃, and continue to react for 5h. Then adjust the solution pH to neutral, filter and add the filtrate to petroleum ether for precipitation, and vacuum dry to obtain BLG-NCA monomer.

[0104] (2) Synthesis of PBLG block copolymers

[0105] Weigh 5g of dried BLG-NCA, add 50mL of anhydrous DMF and mix well, add 0.149mL of pentamethylenediamine, and react at room temperature for 3 days. The polymer solution is precipitated in anhydrous ethanol and dried to obtain a powdery product with a yield of 89%. The molecular weight of the obtained PBLG triblock polymer is 4000-5000.

[0106] (3) Synthesis of spider silk-like polymer PMB

[0107] Weigh 6 g of PTMEG and dry it in vacuum at 80°C for 3 h. Then add 0.65 mL of TDI and 0.06 g of catalyst (butyltin dilaurate). Stir and react at 80°C for 3 h. Then add the DMF solution (5 mL, concentration of 1.0 g / mL) of the PBLG triblock polymer obtained in step (2) and continue the reaction at 80°C for 12 h. The yield of the obtained polymer is 89%. The number average molecular weight of the final polymer is 220,000, where n=27, m=19, x=10, and y=4.

[0108] Example 5

[0109] (1) Synthesis of γ-benzyl-L-glutamate five-membered cyclic anhydride (BLG-NCA)

[0110] Weigh 200g L-glutamic acid and 150mL benzyl alcohol respectively, mix them in 60wt% concentrated sulfuric acid, react at 70℃ for 3h, cool the obtained liquid and adjust the pH to neutral, let it stand and filter to obtain a powdery substance. The product is recrystallized in hot water (~80℃) and vacuum dried to obtain BLG. Weigh 20g BLG, add ethyl acetate, add 1.5 times the molar equivalent of triphosgene solid when heated to 70℃, and continue to react for 5h. Then adjust the solution pH to neutral, filter and add the filtrate to petroleum ether for precipitation, and vacuum dry to obtain BLG-NCA monomer.

[0111] (2) Synthesis of PBLG block copolymers

[0112] Weigh 5g of dried BLG-NCA, add 50mL DMF and mix well, then add 0.149mL of pentamethylenediamine and react at room temperature for 3 days. The polymer solution is precipitated in anhydrous ethanol and dried to obtain a powdery product with a yield of 89%. The molecular weight of the obtained PBLG triblock polymer is 4000-5000.

[0113] (3) Synthesis of spider silk-like polymer PMB

[0114] Weigh 6 g of PTMEG and dry it in vacuum at 80°C for 3 h. Then add 0.75 mL of HDI and 0.06 g of catalyst (butyltin dilaurate). Stir and react at 80°C for 3 h. Then add the DMF solution (5 mL, concentration of 1.0 g / mL) of the PBLG triblock polymer obtained in step (2) and continue the reaction at 80°C for 12 h. The yield of the obtained polymer is 93%. The number average molecular weight of the final polymer is 210,000, where n=27, m=20, x=10, and y=4.

[0115] Comparative Example 1

[0116] Compared with Example 1, no PBLG segment was added during the preparation process. 6 g of PTMEG was weighed and vacuum dried at 80° C. for 3 h. Then, 1.02 mL of IPDI and 0.06 g of catalyst (butyltin dilaurate) were added thereto. The reaction was stirred at 80° C. for 15 h. Finally, only a fluid substance with high viscosity was obtained by precipitation in water. The fluid substance was relatively soft and had no strength and could not be spun.

[0117] Test Example 1

[0118] The preparation of the fibers involved and the related testing methods are as follows:

[0119] The fiber was prepared by wet spinning. First, the polymers in Examples 1-5 were dissolved in hexafluoroisopropanol (HFIP) solvent to prepare a solution with a concentration of 20-50% wt%. The solution was spun in air at a speed of 20uL / min using a syringe pump at an indoor temperature of 25°C and a humidity of 70%. The stretching ratio was 35. The fiber was pre-stretched (400%) and dried by infrared light heating. The fiber stretching test was carried out at a humidity of 60%. The stretching speed during the tensile stress-strain test was 20mm / min, the indoor temperature was 25°C, and the jacket spacing was 20mm. Reference standard GB / T 14337-2008. The test results are shown in the following table:

[0120] Yield (%) Elongation at break (%) <![CDATA[Toughness (MJ / m 3 )]]> Example 1 92 748 382 Example 2 90 703 356 Example 3 89 561 311 Example 4 89 646 355 Example 5 93 768 385

[0121] The spider silk-like polymer material of the present invention has good toughness, high elongation at break, tensile strength of more than 90 MPa, and Young's modulus of more than 71 MPa, thus meeting the use requirements of the spider silk-like material.

[0122] 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 (I): in, p is an integer from 2 to 8 R is A is x is 8, 9, 10, 11 or 12; y is 2, 3, 4, 5 or 6; m is 18, 19, 20, 21, 22, 23 or 24; and n is 24, 25, 26, 27, 28, 29 or 30.

2. The compound according to claim 1, characterized in that p is 5.

3. The compound according to claim 1, characterized in that The compound of formula (I) has the structure shown in formula (I-1): Wherein, p, x, y, m, n, R, and A have the definitions as described in claim 1.

4. A method for preparing the compound according to any one of claims 1 to 3, characterized in that: The following steps are involved: (a) Compound 1 reacts with triphosgene to obtain compound 2; (b) Compound 2 reacts with compound 3 to obtain compound 4; (c) Compound 5 reacts with compound 6 to obtain compound 7; (d) Compound 7 reacts with compound 4 to obtain a compound represented by formula (I); Wherein, p, x, y, m, n, R, and A have the definitions described in any one of claims 1-3.

5. The preparation method according to claim 4, characterized in that: In step (a), the compound 1 in step (a) is selected from glutamic acid, L-glutamic acid, and R-glutamic acid.

6. The preparation method according to claim 4, characterized in that: In step (b), the compound 3 is selected from ethylenediamine, propylenediamine, butylenediamine, pentanediamine, and hexamethylenediamine.

7. The preparation method according to claim 4, characterized in that: In step (b), the molecular weight of the compound 4 is 200-5000.

8. The preparation method according to claim 4, characterized in that: In step (b), the molecular weight of compound 4 is 500-2000.

9. The preparation method according to claim 4, characterized in that: In step (c), a catalyst is added to the reaction, and the catalyst is selected from at least one of trimethyltin, trimethyltin chloride, triethyltin, butyltin dilaurate, triethyltin chloride, triethyltin bromide, triethyltin iodide, triethyltin hydroxide, triethyltin sulfate, bistriethyltin sulfate, tributyltin chloride, triphenyltin chloride, triphenyltin acetate, tetraethyltin, tetrabutyltin, tetraphenyltin, and triethyltin sulfate.

10. The preparation method according to claim 4, characterized in that: The compound 6 in step (c) is at least one of methylene diisocyanate (HDI).

11. The preparation method according to claim 4, characterized in that: Step (a) further comprises step (a'): compound 1 reacts with benzyl alcohol to obtain compound 1', and compound 1' further reacts with step (a) to obtain compound 2; the compound 1' is benzyl glutamate.

12. Use of the compound represented by formula 4 in the preparation of the compound of formula (I) according to any one of claims 1 to 3; in, R has the definition as defined in any one of claims 1 to 3.

13. Use of the compound according to any one of claims 1 to 3 as a bionic material.

14. Use of the compound according to any one of claims 1 to 3 as a spider silk imitating material.

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