Polymer, modified polyurethane elastomer and method for producing the same

Abstract

The application provides a polymer, a modified polyurethane elastomer and a preparation method thereof, and relates to the technical field of polymers.The polymer has a polymer main chain containing a large number of quaternary carbon-quaternary carbon covalent bonds, so that the polymer has a relatively high response breaking property to stress and heat.The application also provides a modified polyurethane elastomer which is mainly prepared from diisocyanate, diol, modified crosslinking agent and catalyst and the like raw materials, wherein the polymer is used as the modified crosslinking agent, the modified crosslinking agent main chain skeleton contains more methylol groups, and through condensation crosslinking reaction with diisocyanate and diol, crosslinking can be introduced into the two-dimensional inter-chain of the polyurethane elastomer.This kind of modified polyurethane elastomer can realize self-repairing and self-strengthening when subjected to mechanical force and heat, the modified crosslinking agent skeleton in the framework breaks and recombines through quaternary carbon-quaternary carbon covalent bond, and then self-repairing and self-strengthening are realized through addition of free radicals after breaking and secondary crosslinking.

Description

Technical Field

[0001] This invention relates to the field of polymer material synthesis technology, and in particular to a polymer, a modified polyurethane elastomer, and a method for preparing the same. Background Technology

[0002] Polyurethane and other elastomeric materials have extremely wide applications in engineering, construction, and manufacturing. However, under certain working conditions where the shear stress exceeds the material's ultimate limit, these elastomeric materials may undergo irreversible structural yielding and fracture to a certain extent, leading to a significant decrease in the mechanical properties of the components.

[0003] By introducing stress-sensitive groups (stress-sensitive structural units) with dynamic covalent bonds into the framework of this series of elastomer materials through copolymerization or post-modification, the initial material can be modified. These stress-sensitive groups in the modified elastomers fracture under stress, and then release the polymer stress through energy dissipation and reversible covalent bond recombination. After stress removal, these elastomers can also achieve damage self-repair and stress-activated self-reinforcement functions through the recombination of fracture stress-sensitive groups and secondary crosslinking. These functions can alleviate a series of problems existing in the aforementioned elastomer materials.

[0004] Some reported mechanistic groups include dicyanobis(fluorenyl)-, diselenoyl, 1,2-dioxane, and ferrocene. Elastomers modified with these mechanistic groups either require the introduction of other secondary crosslinking sites to achieve damage self-repair and self-reinforcement functions, or they do not possess these functions.

[0005] In view of this, the present invention is hereby proposed. Summary of the Invention

[0006] The purpose of this invention is to provide a polymer, a modified polyurethane elastomer, and a method for preparing the same. The polymer is used as a crosslinking agent to prepare the modified polyurethane elastomer, which enables the modified polyurethane elastomer to have damage self-repair and self-reinforcing properties. This solves the technical problem that existing force-sensitive group modified elastomer materials require the introduction of other secondary crosslinking points to achieve damage self-repair and self-reinforcing functions or do not have self-repair and self-reinforcing functions at all.

[0007] To achieve the above objectives, the present invention adopts the following technical solution:

[0008] This invention provides a polymer, the structural formula of which is shown in formula (1):

[0009]

[0010] Where R is selected from any one of hydrogen, hydrocarbon, alkoxy, aryl, or halogen, and n represents the degree of polymerization.

[0011] Furthermore, based on the above technical solution of the present invention, in formula (1), R is selected from any one of hydrogen, alkyl, alkoxy, phenyl or halogen, and n is any integer between 20 and 30;

[0012] Preferably, in formula (1), R is selected from any one of hydrogen, methyl, methoxy, phenyl or chlorine, and n is any integer between 20 and 30.

[0013] The present invention also provides a method for preparing the above-mentioned polymer, comprising the following steps:

[0014] The polymer was obtained by reacting 4-ethynyl-4-aryl-1,3-dioxa-2-cyclopentanone, a copper reagent, and an organophosphine ligand in a solvent.

[0015] Furthermore, based on the above technical solution of the present invention, the molar ratio of 4-ethynyl-4-aryl-1,3-dioxa-2-cyclopentanone, copper reagent and organophosphorus ligand is (100-200):1:1;

[0016] And / or, the copper reagent comprises copper acetylide and / or a copper salt; preferably, the copper acetylide comprises at least one of copper phenylpropyne, copper 4-trifluoromethylphenylpropyne, or copper 4-methoxyphenylpropyne; preferably, the copper salt comprises at least one of copper tetraacetonitrile hexafluorophosphate, cuprous iodide, cuprous bromide, cuprous chloride, or cuprous cyanide.

[0017] And / or, the organophosphine ligand comprises at least one of 2-bicyclohexylphosphine-2',4',6'-triisopropylbiphenyl, triphenylphosphine, tri-n-butylphosphine, tricyclohexylphosphine, 1,2-(diphenylphosphine)ethane, or 1,3-(diphenylphosphine)propane.

[0018] Furthermore, based on the above technical solution of the present invention, the reaction temperature is 40-60℃ and the time is 24-48h;

[0019] And / or, the solvent for the reaction includes anhydrous dimethyl sulfoxide;

[0020] And / or, after the reaction, a purification step is also included to obtain the polymer.

[0021] The present invention also provides a modified crosslinking agent, which comprises a polymer obtained by the above-described preparation method.

[0022] The present invention also provides a modified polyurethane elastomer, which is mainly prepared from the following raw materials:

[0023] Diisocyanate, glycol, modified crosslinking agent and catalyst;

[0024] The modified crosslinking agent is the aforementioned modified crosslinking agent.

[0025] Furthermore, based on the above-mentioned technical solution of the present invention, the mass ratio of the diisocyanate, diol, modified crosslinking agent and catalyst is (6-15):(81-93):(0.5-4):5;

[0026] And / or, the diol includes long-chain diols and short-chain diols;

[0027] The long-chain diol includes at least one of polytetramethylene ether diol, polyethylene glycol, or polycaprolactone diol;

[0028] The short-chain diol includes at least one of butanediol and pentanediol;

[0029] And / or, the diisocyanate comprises at least one of 4,4'-diisocyanate diphenylmethane, 1,4-phenyl diisocyanate, toluene-2,4-diisocyanate or 1,2-phenyl diisocyanate;

[0030] And / or, the catalyst comprises at least one of dibutyltin dilaurate, a tertiary amine, an organozinc reagent, or an organobismuth reagent;

[0031] The tertiary amine includes 1,4-diazabicyclo[2,2,2]octene;

[0032] The organic zinc reagent includes zinc diethyldithiocarbamate;

[0033] The organic bismuth reagent includes at least one of bismuth trioctanoate and bismuth neodecanoate.

[0034] The present invention also provides a method for preparing the above-mentioned modified polyurethane elastomer, comprising the following steps:

[0035] A modified polyurethane elastomer is obtained by crosslinking a diol, a diisocyanate, and a modified crosslinking agent under the catalysis of a catalyst.

[0036] Furthermore, based on the above technical solution of the present invention, the temperature of the crosslinking reaction is 20-30℃;

[0037] And / or, the crosslinking reaction takes 12-24 hours.

[0038] The technical solution of the present invention has the following advantages compared with the prior art:

[0039] 1. The present invention provides a polymer having a polymer backbone containing a large number of quaternary carbon-quaternary carbon covalent bonds, thereby giving the polymer high stress and heat-responsive fracture properties.

[0040] 2. The present invention also provides a modified crosslinking agent, which, given the properties of the above-mentioned polymer, can be used as a modified crosslinking agent in the preparation of elastomer materials, thereby imparting corresponding properties to the elastomer materials.

[0041] 3. This invention provides a modified polyurethane elastomer, mainly prepared from raw materials such as diisocyanate, glycol, modified crosslinking agent, and catalyst. The aforementioned polymer is used as the modified crosslinking agent, whose main chain backbone contains a large number of hydroxymethyl groups. Through condensation crosslinking reactions with diisocyanate and glycol, crosslinking can be introduced into the two-dimensional interchain structures of the polyurethane elastomer. When subjected to mechanical and thermal forces, this type of modified polyurethane elastomer undergoes quaternary carbon-quaternary carbon covalent bond breakage and recombination within the modified crosslinking agent backbone. Subsequently, through free radical addition and secondary crosslinking after the breakage, damage self-repair and self-reinforcement are achieved. Attached Figure Description

[0042] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0043] Figure 1 The nuclear magnetic resonance spectrum of 4-ethynyl-4-phenyl-1,3-dioxa-2-cyclopentanone obtained in Example 1 of the present invention;

[0044] Figure 2 This is a gel permeation chromatogram of the polymer obtained in Example 1 of the present invention;

[0045] Figure 3 The nuclear magnetic resonance spectrum of the polymer obtained in Example 1 of this invention;

[0046] Figure 4 The nuclear magnetic resonance spectrum of 4-ethynyl-4-(4-methoxyphenyl)-1,3-dioxa-2-cyclopentanone obtained in Example 2 of this invention;

[0047] Figure 5 This is a gel permeation chromatogram of the polymer obtained in Example 2 of the present invention;

[0048] Figure 6 The nuclear magnetic resonance spectrum of the polymer obtained in Example 2 of this invention;

[0049] Figure 7 The nuclear magnetic resonance spectrum of 4-ethynyl-4-(4-methylphenyl)-1,3-dioxa-2-cyclopentanone obtained in Example 3 of this invention;

[0050] Figure 8 This is a gel permeation chromatogram of the polymer obtained in Example 3 of the present invention;

[0051] Figure 9 The nuclear magnetic resonance spectrum of the polymer obtained in Example 3 of this invention;

[0052] Figure 10 The nuclear magnetic resonance spectrum of 4-ethynyl-4-(4-chlorophenyl)-1,3-dioxa-2-cyclopentanone obtained in Example 4 of this invention;

[0053] Figure 11 This is a gel permeation chromatogram of the polymer obtained in Example 4 of the present invention;

[0054] Figure 12 The nuclear magnetic resonance spectrum of the polymer obtained in Example 4 of this invention;

[0055] Figure 13 The nuclear magnetic resonance spectrum of 4-ethynyl-4-(4-biphenyl)-1,3-dioxa-2-cyclopentanone obtained in Example 5 of this invention;

[0056] Figure 14 This is a gel permeation chromatogram of the polymer obtained in Example 5 of the present invention;

[0057] Figure 15 The nuclear magnetic resonance spectrum of the polymer obtained in Example 5 of this invention;

[0058] Figure 16 The nuclear magnetic resonance spectrum of 1,1'-(1,4-phenylene)bis(prop-2-yn-1-ol) obtained in Comparative Example 1 of this invention;

[0059] Figure 17 This is a schematic diagram of a method for testing the damage self-repair and self-reinforcement of the modified polyurethane elastomer obtained in Example 6 of the present invention.

[0060] Figure 18 The images show uniaxial stress-strain test results of the modified polyurethane elastomer obtained in Example 6 of this invention before and after damage repair.

[0061] Figure 19 The images show uniaxial stress-strain test results of the modified polyurethane elastomer obtained in Example 7 of this invention before and after damage repair.

[0062] Figure 20 The images show uniaxial stress-strain test results of the modified polyurethane elastomer obtained in Example 8 of this invention before and after damage repair.

[0063] Figure 21 The images show uniaxial stress-strain test results of the modified polyurethane elastomer obtained in Example 9 of this invention before and after damage repair.

[0064] Figure 22 The modified polyurethane elastomer obtained in Example 6 of this invention is shown in the cyclic uniaxial stress-strain test diagram.

[0065] Figure 23 The image shows the cyclic uniaxial stress-strain test results of the modified polyurethane elastomer obtained in Comparative Example 1 of this invention. Detailed Implementation

[0066] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions in the embodiments of this invention will be clearly and completely described below in conjunction with the embodiments of this invention. Those skilled in the art should understand that the embodiments described are merely illustrative of the invention and should not be considered as specific limitations thereof. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention. Process parameters not specifically specified in the following embodiments are generally performed under conventional conditions.

[0067] The endpoints and any values ​​of the ranges disclosed in this invention are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this invention.

[0068] According to a first aspect of the present invention, a polymer is provided, which is poly(1,2,3,4,5-hexaptenene) having the structural formula shown in formula (1):

[0069]

[0070] Where R is selected from any one of hydrogen, hydrocarbon, alkoxy, aryl, or halogen, and n represents the degree of polymerization.

[0071] It should be noted that hydrocarbon groups refer to substituted or unsubstituted hydrocarbon groups, such as substituted or unsubstituted alkyl groups, substituted or unsubstituted alkenyl groups, etc.; alkoxy groups refer to substituted or unsubstituted alkoxy groups, such as methoxy, ethoxy, etc.; aryl groups are such as phenyl or substituted phenyl groups; halogens are such as fluorine, chlorine, bromine or iodine, etc.

[0072] As can be seen from the above structural formula, the main chain of the polymer contains a large number of quaternary carbon-quaternary carbon covalent bonds. When subjected to mechanical and / or thermal forces, these covalent bonds will break and recombine, thus giving the polymer a high stress and heat response fracture property.

[0073] Furthermore, the polymer backbone contains a large amount of hydroxymethyl groups, which can undergo condensation crosslinking reactions with cyanate esters and alcohols, providing a basis for its subsequent application (as a modified crosslinking agent for polyurethane elastomers).

[0074] As an optional embodiment of the present invention, in formula (1), R is selected from any one of hydrogen, alkyl, alkoxy, phenyl or halogen, and n is any integer between 20 and 30; for example, n is 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30.

[0075] In a preferred embodiment of the present invention, in formula (1), R is selected from any one of hydrogen, methyl, methoxy, phenyl or chlorine, and n is any integer between 20 and 30; for example, n is 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30.

[0076] Preferably, the polymer comprises at least one of the following polymers having the following structural formulas:

[0077]

[0078] Where n is any integer between 20 and 30, such as 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30.

[0079] According to a second aspect of the present invention, the present invention also provides a method for preparing the above-mentioned polymer, comprising the following steps:

[0080] The polymer was obtained by reacting 4-ethynyl-4-aryl-1,3-dioxa-2-cyclopentanone, a copper reagent, and an organophosphine ligand.

[0081] This preparation method is currently the only synthetic route for preparing this type of poly(1,2,3,4,5-hexaptenene). It requires fewer substrate synthesis steps, has a high yield, and does not use toxic or harmful catalysts or reactants.

[0082] The chemical reaction formulas involved in the above preparation process are shown in formula (2):

[0083]

[0084] In formula (2), the copper reagent used is specifically copper phenylpropyne, but it is not limited to this. Similarly, the solvent, reaction time, and reaction temperature used in formula (2) are not limited to this.

[0085] As an optional embodiment of the present invention, the molar ratio of 4-ethynyl-4-aryl-1,3-dioxa-2-cyclopentanone, copper reagent and organophosphorus ligand is (100-200):1:1; typical but non-limiting molar ratios are 100:1:1, 120:1:1, 140:1:1, 150:1:1, 160:1:1, 180:1:1 or 200:1:1, etc.

[0086] As an optional embodiment of the present invention, the copper reagent includes copper acetylenicide and / or copper salt.

[0087] In a preferred embodiment of the present invention, the copper acetylide includes at least one of copper phenylpropyne, copper 4-trifluoromethylphenylpropyne, or copper 4-methoxyphenylpropyne.

[0088] In a preferred embodiment of the present invention, the copper salt includes at least one of copper tetraacetonitrile hexafluorophosphate, cuprous iodide, cuprous bromide, cuprous chloride, or cuprous cyanide.

[0089] As an optional embodiment of the present invention, the organophosphine ligand includes at least one selected from 2-bicyclohexylphosphine-2',4',6'-triisopropylbiphenyl, triphenylphosphine, tri-n-butylphosphine, tricyclohexylphosphine, 1,2-(diphenylphosphine)ethane, or 1,3-(diphenylphosphine)propane.

[0090] In this invention, copper acetylide and its copper salt act as key catalysts in the reaction, binding with organophosphorus ligands to exert their effects. The organophosphorus ligands also act as key ligands in the reaction, binding with copper to exert their effects.

[0091] As an optional embodiment of the present invention, the reaction temperature is 40-60°C and the time is 24-48h; typical but non-limiting reaction temperatures are 40°C, 42°C, 45°C, 48°C, 50°C, 52°C, 55°C, 58°C or 60°C and any range between any two points, and typical but non-limiting times are 24h, 28h, 30h, 32h, 36h, 38h, 40h, 42h, 45h or 48h and any range between any two points.

[0092] As an optional embodiment of the present invention, the solvent for the reaction is anhydrous dimethyl sulfoxide.

[0093] As an optional embodiment of the present invention, after the reaction, purification (precipitation separation) is performed to obtain the polymer.

[0094] In this invention, 4-ethynyl-4-aryl-1,3-dioxa-2-cyclopentanone is commercially available or can be prepared by the manufacturer. As an optional embodiment of this invention, the preparation method of 4-ethynyl-4-aryl-1,3-dioxa-2-cyclopentanone includes the following steps:

[0095] 2-Arylbut-3-yne-1,2-diol, carbonyl diimidazole (CDI), 4-dimethylaminopyridine (DMAP), and triethylamine (TEA) were reacted to give 4-ethynyl-4-aryl-1,3-dioxa-2-cyclopentanone.

[0096] As an optional embodiment of the present invention, the molar ratio of 2-arylbut-3-yne-1,2-diol, carbonyl diimidazole, 4-dimethylaminopyridine and triethylamine is 10:(10-20):(1-5):(30-100), and typical but non-limiting molar ratios are 10:10:1:30, 10:15:1:30, 10:20:1:30, 10:10:2:30, 10:10:5:30, 10:10:1:50, 10:10:1:60, 10:10:1:80, 10:10:1:100, 10:20:2:30, 10:20:2:50, 10:20:2:80, 10:20:2:100 or 10:20:5:100, etc.

[0097] As an optional embodiment of the present invention, in the method for preparing 4-ethynyl-4-aryl-1,3-dioxa-2-cyclopentanone, the reaction temperature is room temperature and the time is 5-12h (e.g., 5h, 6h, 8h, 10h or 12h, etc.).

[0098] And / or, the reaction is carried out in dichloromethane;

[0099] And / or, after the reaction, extraction and separation by column chromatography were performed to obtain 4-ethynyl-4-aryl-1,3-dioxa-2-cyclopentanone.

[0100] In the preparation method of 4-ethynyl-4-aryl-1,3-dioxa-2-cyclopentanone of the present invention, dimethyl carbonate or di-tert-butyl carbonate can be used instead of carbonyl diimidazole, and organic bases such as tributylamine or 1,8-diazabicyclo[5.4.0]undec-7-ene can be used instead of triethylamine.

[0101] As an optional embodiment of the present invention, the preparation method of 2-arylbut-3-yne-1,2-diol includes the following steps: reacting α-hydroxyaryl ketone and ethynyl magnesium bromide to obtain 2-arylbut-3-yne-1,2-diol.

[0102] As an optional embodiment of the present invention, the molar ratio of α-hydroxyacetone and ethynyl magnesium bromide is 1:(2-3); typical but non-limiting molar ratios are 1:2, 1:2.2, 1:2.4, 1:2.5, 1:2.6, 1:2.8 or 1:3.

[0103] As an optional embodiment of the present invention, in the method for preparing 2-arylbut-3-yne-1,2-diol, the reaction temperature is room temperature (e.g., 15-30°C) and the time is 12-24 h; typical but non-limiting reaction times are 12 h, 15 h, 18 h, 20 h, 22 h or 24 h.

[0104] And / or, the reaction takes place in tetrahydrofuran;

[0105] And / or, after the reaction, extraction and solvent evaporation are performed.

[0106] In the preparation method of 2-arylbut-3-yne-1,2-diol of the present invention, acetylenol lithium can be used instead of acetylenol magnesium bromide.

[0107]

[0108] Reaction formula (3) is the chemical reaction formula for the preparation of 2-arylbut-3-yne-1,2-diol and 4-ethynyl-4-aryl-1,3-dioxa-2-cyclopentanone.

[0109] According to a third aspect of the present invention, the present invention provides the above-described polymer or the polymer obtained by the above-described preparation method as a modified crosslinking agent.

[0110] Given the properties of the aforementioned polymers, they can be used as modified crosslinking agents in the preparation of elastomer materials.

[0111] According to a fourth aspect of the present invention, the present invention also provides a modified polyurethane elastomer, which is prepared from the following raw materials:

[0112] The mixture comprises diisocyanate, diol, modified crosslinking agent, and catalyst, wherein the modified crosslinking agent is the polymer described above or a polymer prepared by the method described above.

[0113] The modified crosslinking agent undergoes a bulk crosslinking reaction with diol and diisocyanate to obtain a modified polyurethane elastomer. Given that the modified crosslinking agent provided by this invention has a polymer backbone containing a large number of quaternary carbon-quaternary carbon covalent bonds, it exhibits high stress and heat-responsive fracture properties. By using it as a modified crosslinking agent for elastomer materials, a series of parent elastomer polymers can possess damage self-repair and self-reinforcing functions through self-secondary crosslinking without the introduction of crosslinking points.

[0114] In one optional embodiment of the present invention, the mass ratio of diisocyanate, diol, modified crosslinking agent, and catalyst is (6-15):(81-93):(0.5-4):5. Typical but non-limiting mass ratios are 6:85:1:5, 6:92:2:5, 6.1:92.1:1.8:5, 6:90:4:5, 10:86:4:5, 10:88:2:5, 11:84:0.5:5, 11:88:0.5:5, 11:88:1:5, 11:88:2:5, 11:88:3:5, 11.5:87.8:0.7:5, 12:84:0.5:5, and 12:88:0. 5:5, 12:88:1:5, 12:88:2:5, 12:88:3:5, 12.2:85.7:2.1:5, 13:84:0.5:5, 13:88:0.5:5, 13:88:1:5, 13:88:2:5, 13:88:3:5, 13:83:4:5, 14:82:4:5, 14.8:81.2:4:5, 15:81:4:5 or 14.9:81.3:3.8:5.

[0115] As an optional embodiment of the present invention, the diol includes long-chain diols and short-chain diols.

[0116] Preferably, the long-chain diol includes at least one of polytetramethylene ether glycol, polyethylene glycol, or polycaprolactone diol. Polycaprolactone diol is a polycaprolactone capped with ethylene glycol, and is therefore also known as polycaprolactone-ethylene glycol.

[0117] Preferably, the short-chain diols include butanediol and / or pentanediol.

[0118] As an optional embodiment of the present invention, the diisocyanate includes at least one of 4,4'-diisocyanate diphenylmethane, 1,4-phenyl diisocyanate, toluene-2,4-diisocyanate or 1,2-phenyl diisocyanate.

[0119] As an optional embodiment of the present invention, the catalyst includes at least one of dibutyltin dilaurate, a tertiary amine, or an organozinc reagent.

[0120] Preferably, the tertiary amine includes 1,4-diazabicyclo[2,2,2]octene;

[0121] Preferably, the organozinc reagent includes zinc diethyldithiocarbamate;

[0122] Preferably, the organic bismuth reagent includes at least one of bismuth trioctanoate or bismuth neodecanoate.

[0123] According to a fifth aspect of the present invention, the present invention provides a method for preparing the above-described modified polyurethane elastomer, comprising the following steps:

[0124] A modified polyurethane elastomer is obtained by crosslinking a diol, a diisocyanate, and a modified crosslinking agent under the catalysis of a catalyst.

[0125] As an optional embodiment of the present invention, the temperature of the crosslinking reaction is 20-30°C; typical but non-limiting reaction temperatures are 20°C, 22°C, 24°C, 25°C, 26°C, 28°C or 30°C and any range between any two points.

[0126] As an optional embodiment of the present invention, the crosslinking reaction time is 12-24h, and the typical but non-limiting reaction time is 12h, 15h, 16h, 18h, 20h or 24h and any numerical range between any two points.

[0127] The present invention will now be described in further detail with reference to specific embodiments and comparative examples.

[0128] Example 1

[0129] This embodiment provides a polymer having the following chemical structure:

[0130] Where n is 28-30.

[0131] The preparation method of this polymer includes the following steps:

[0132] S1: Under N2 protection, α-hydroxyphenylacetone was added to the reactor according to the feed ratio, followed by anhydrous tetrahydrofuran. A tetrahydrofuran solution of ethynyl magnesium bromide was then added under ice bath conditions. After the feed was complete, the mixture was stirred for 12 hours (the molar ratio of α-hydroxyphenylacetone to ethynyl magnesium bromide was 1:2). The mixture was quenched with saturated ammonium chloride solution and extracted with ethyl acetate. After drying, the solvent was removed under reduced pressure. The crude product, 2-phenylbut-3-yne-1,2-diol, was used directly in the next reaction without further treatment.

[0133] S2: Carbonyl diimidazole, 4-dimethylaminopyridine, and triethylamine were dissolved in tetrahydrofuran at the feed ratio. The crude product 2-phenylbut-3-yne-1,2-diol obtained in the previous step was added under stirring at room temperature and reacted for 5 h (the molar ratio of 2-phenylbut-3-yne-1,2-diol, carbonyl diimidazole, 4-dimethylaminopyridine, and triethylamine was 10:10:1:30). The imidazole was then washed with citric acid aqueous solution, followed by extraction three times with dichloromethane. The organic phase was dried over anhydrous sodium sulfate, filtered to remove the solvent, concentrated under reduced pressure, and the product was purified by column chromatography to obtain 4-ethynyl-4-phenyl-1,3-dioxa-2-cyclopentanone.

[0134] The prepared 4-ethynyl-4-phenyl-1,3-dioxa-2-cyclopentanone was subjected to nuclear magnetic resonance, and the results are as follows: Figure 1 As shown. Among them, Figure 1 The image shows the 1H-NMR spectrum of 4-ethynyl-4-phenyl-1,3-dioxa-2-cyclopentanone. The horizontal axis represents the chemical shift, the vertical axis represents the absorption intensity, and the integrated area under the peak represents the number of active hydrogens.

[0135] S3: Under nitrogen protection, 4-ethynyl-4-phenyl-1,3-dioxa-2-cyclopentanone, anhydrous dimethyl sulfoxide, copper phenylpropyne, and X-Phos ligand (molar ratio of 4-ethynyl-4-phenyl-1,3-dioxa-2-cyclopentanone, copper phenylpropyne, and X-Phos ligand is 200:1:1) synthesized in the previous step were added to the reaction tube in the following order: The system was then stirred at 50°C for 24 h to carry out the reaction. The reaction formula is shown below:

[0136]

[0137] After the reaction was completed, the reaction system was extracted with tetrahydrofuran and dried, and then purified by precipitation in n-pentane to obtain a crude polymer sample. The crude sample was redissolved with a small amount of THF and purified by precipitation and filtration in n-pentane (this operation was repeated several times) to obtain the polymer (poly(2,7-diphenyl-1,8-dihydroxy-2,3,4,5,6-octapene)).

[0138] The obtained polymer was subjected to gel permeation chromatography and nuclear magnetic resonance, and the results are as follows: Figure 2 and Figure 3 As shown. Among them, Figure 2 This is a size exclusion-gel permeation chromatogram of the polymer. The horizontal axis represents retention time, which is inversely proportional to molecular weight according to the standard polystyrene calibration curve. The vertical axis represents the refractive index factor, which is directly proportional to the number of polymer molecules. This graph reflects the molecular weight distribution and allows for the calculation of the degree of polymerization range. Figure 3 The graph shows the 1H-NMR spectrum of the polymer. The horizontal axis represents the chemical shift, the vertical axis represents the absorption intensity, and the integrated area under the peak represents the number of active hydrogen atoms.

[0139] Example 2

[0140] This embodiment provides a polymer having the following chemical structure:

[0141] Where n is 21-23.

[0142] The preparation method of this polymer includes the following steps:

[0143] S1: Under N2 protection, α-hydroxy-4-methoxyphenylacetone was added to the reactor according to the feed ratio, followed by anhydrous tetrahydrofuran. A tetrahydrofuran solution of ethynyl magnesium bromide was then added under ice bath conditions. After the feed was complete, the mixture was stirred for 12 hours (the molar ratio of α-hydroxy-4-methoxyphenylacetone to ethynyl magnesium bromide was 1:2). The mixture was quenched with saturated ammonium chloride aqueous solution and extracted with ethyl acetate. After drying, the solvent was removed under reduced pressure. The crude product, 2-(4-methoxyphenyl)-but-3-yne-1,2-diol, was used directly in the next reaction without further treatment.

[0144] S2: Carbonyl diimidazole, 4-dimethylaminopyridine, and triethylamine were dissolved in tetrahydrofuran at the feed ratio. The crude product 2-(4-methoxyphenyl)-but-3-yne-1,2-diol obtained in the previous step was added under stirring at room temperature and reacted for 5 h (the molar ratio of 2-(4-methoxyphenyl)-but-3-yne-1,2-diol, carbonyl diimidazole, 4-dimethylaminopyridine, and triethylamine was 10:10:1:30). After washing the imidazole with citric acid aqueous solution, the mixture was extracted three times with dichloromethane. The organic phase was dried with anhydrous sodium sulfate, filtered to remove the solvent under reduced pressure, and the product was purified by column chromatography to obtain 4-ethynyl-4-(4-methoxyphenyl)-1,3-dioxa-2-cyclopentanone. The prepared 4-ethynyl-4-(4-methoxyphenyl)-1,3-dioxa-2-cyclopentanone was subjected to nuclear magnetic resonance (NMR), and the results are as follows: Figure 4 As shown;

[0145] in, Figure 4 The image shows the 1H-NMR spectrum of 4-ethynyl-4-(4-methoxyphenyl)-1,3-dioxa-2-cyclopentanone. The horizontal axis represents the chemical shift, the vertical axis represents the absorption intensity, and the integrated area under the peak represents the number of active hydrogens.

[0146] S3: Under nitrogen protection, 4-ethynyl-4-(4-methoxyphenyl)-1,3-dioxa-2-cyclopentanone, anhydrous dimethyl sulfoxide, copper phenylpropyne, and X-Phos ligand (molar ratio of 4-ethynyl-4-(4-methoxyphenyl)-1,3-dioxa-2-cyclopentanone, copper phenylpropyne, and X-Phos ligand is 200:1:1) synthesized in the previous step were added to the reaction tube in the following ratio: The system was then stirred at 50°C for 24 h. The reaction formula is shown below:

[0147]

[0148] After the reaction was completed, the reaction system was extracted with tetrahydrofuran and dried, and then purified by precipitation in n-pentane to obtain a crude polymer sample. The crude sample was redissolved again with a small amount of THF and purified by precipitation and filtration in n-pentane (this operation was repeated several times) to obtain the polymer (poly(2,7-di(4-methoxyphenyl)-1,8-dihydroxy-2,3,4,5,6-octapene)).

[0149] The obtained polymer was subjected to gel permeation chromatography and nuclear magnetic resonance, and the results are as follows: Figure 5 and Figure 6 As shown. Among them, Figure 5 This is a size exclusion-gel permeation chromatogram of the polymer. The horizontal axis represents retention time, which is inversely proportional to molecular weight according to the standard polystyrene calibration curve. The vertical axis represents the refractive index factor, which is directly proportional to the number of polymer molecules. Figure 6 The graph shows the 1H-NMR spectrum of the polymer. The horizontal axis represents the chemical shift, the vertical axis represents the absorption intensity, and the integrated area under the peak represents the number of active hydrogen atoms.

[0150] Example 3

[0151] This embodiment provides a polymer having the following chemical structure:

[0152] Where n is 22-25.

[0153] The preparation method of this polymer includes the following steps:

[0154] S1: Under N2 protection, α-hydroxy-4-methylphenylacetone was added to the reactor according to the feed ratio, followed by anhydrous tetrahydrofuran. A tetrahydrofuran solution of ethynyl magnesium bromide was then added under ice bath conditions. After the feed was complete, the mixture was stirred for 12 hours (the molar ratio of α-hydroxy-4-methylphenylacetone to ethynyl magnesium bromide was 1:2). The mixture was quenched with saturated ammonium chloride aqueous solution and extracted with ethyl acetate. After drying, the solvent was removed under reduced pressure. The crude product, 2-(4-methylphenyl)-but-3-yne-1,2-diol diol, was used directly in the next reaction without further processing.

[0155] S2: Carbonyl diimidazole, 4-dimethylaminopyridine, and triethylamine were dissolved in tetrahydrofuran at the feed ratio. The crude product 2-(4-methylphenyl)-but-3-yne-1,2-diol obtained in the previous step was added under stirring at room temperature and reacted for 5 h (the molar ratio of 2-(4-methylphenyl)-but-3-yne-1,2-diol, carbonyl diimidazole, 4-dimethylaminopyridine, and triethylamine was 10:10:1:30). After washing the imidazole with citric acid aqueous solution, the mixture was extracted three times with dichloromethane. The organic phase was dried over anhydrous sodium sulfate, filtered to remove the solvent, concentrated under reduced pressure, and the product was purified by column chromatography to obtain 4-ethynyl-4-(4-methylphenyl)-1,3-dioxa-2-cyclopentanone.

[0156] The prepared 4-ethynyl-4-(4-methylphenyl)-1,3-dioxa-2-cyclopentanone was subjected to NMR, and the results are as follows: Figure 7 As shown. Figure 7 The image shows the 1H-NMR spectrum of 4-ethynyl-4-(4-methylphenyl)-1,3-dioxa-2-cyclopentanone. The horizontal axis represents the chemical shift, the vertical axis represents the absorption intensity, and the integrated area under the peak represents the number of active hydrogens.

[0157] S3: Under nitrogen protection, 4-ethynyl-4-(4-methylphenyl)-1,3-dioxa-2-cyclopentanone, anhydrous dimethyl sulfoxide, copper phenylpropyne, and X-Phos ligand (molar ratio of 4-ethynyl-4-(4-methylphenyl)-1,3-dioxa-2-cyclopentanone, copper phenylpropyne, and X-Phos ligand is 200:1:1) synthesized in the previous step were added to the reaction tube in the following ratio: The system was then stirred at 50°C for 24 h. The reaction formula is shown below:

[0158]

[0159] After the reaction was completed, the reaction system was extracted with tetrahydrofuran and dried, and then purified by precipitation in n-pentane to obtain a crude polymer sample. The crude sample was redissolved again with a small amount of THF and purified by precipitation and filtration in n-pentane (this operation was repeated several times) to obtain the polymer (poly(2,7-di(4-methylphenyl)-1,8-dihydroxy-2,3,4,5,6-octapene)).

[0160] The obtained polymer was subjected to gel permeation chromatography and nuclear magnetic resonance, and the results are as follows: Figure 8 and Figure 9 As shown. Among them, Figure 8 This is a size exclusion-gel permeation chromatogram of the polymer. The horizontal axis represents retention time, which is inversely proportional to molecular weight according to the standard polystyrene calibration curve. The vertical axis represents the refractive index factor, which is directly proportional to the number of polymer molecules. Figure 9The graph shows the 1H-NMR spectrum of the polymer. The horizontal axis represents the chemical shift, the vertical axis represents the absorption intensity, and the integrated area under the peak represents the number of active hydrogen atoms.

[0161] Example 4

[0162] This embodiment provides a polymer having the following chemical structure:

[0163] Where n is 24-27.

[0164] The preparation method of this polymer includes the following steps:

[0165] S1: Under N2 protection, α-hydroxy-4-chlorophenylacetone was added to the reactor according to the feed ratio, followed by anhydrous tetrahydrofuran. A tetrahydrofuran solution of ethynyl magnesium bromide was then added under ice bath conditions. After the feed was complete, the mixture was stirred for 12 hours (the molar ratio of α-hydroxy-4-chlorophenylacetone to ethynyl magnesium bromide was 1:2). The mixture was quenched with saturated ammonium chloride aqueous solution and extracted with ethyl acetate. After drying, the solvent was removed under reduced pressure. The crude product, 2-(4-chlorophenyl)-but-3-yne-1,2-diol, was used directly in the next reaction without further processing.

[0166] S2: Carbonyl diimidazole, 4-dimethylaminopyridine, and triethylamine were dissolved in tetrahydrofuran at the feed ratio. The crude product 2-(4-chlorophenyl)-but-3-yne-1,2-diol obtained in the previous step was added under stirring at room temperature and reacted for 5 h (the molar ratio of 2-(4-chlorophenyl)-but-3-yne-1,2-diol, carbonyl diimidazole, 4-dimethylaminopyridine, and triethylamine was 10:10:1:30). After washing the imidazole with citric acid aqueous solution, the mixture was extracted three times with dichloromethane. The organic phase was dried over anhydrous sodium sulfate, filtered to remove the solvent, concentrated under reduced pressure, and the product was purified by column chromatography to obtain 4-ethynyl-4-(4-chlorophenyl)-1,3-dioxa-2-cyclopentanone.

[0167] The prepared 4-ethynyl-4-(4-chlorophenyl)-1,3-dioxa-2-cyclopentanone was subjected to NMR, and the results are as follows: Figure 10 As shown. Among them, Figure 10 The image shows the 1H-NMR spectrum of 4-ethynyl-4-(4-chlorophenyl)-1,3-dioxa-2-cyclopentanone. The horizontal axis represents the chemical shift, the vertical axis represents the absorption intensity, and the integrated area under the peak represents the number of active hydrogens.

[0168] S3: Under nitrogen protection, 4-ethynyl-4-(4-chlorophenyl)-1,3-dioxa-2-cyclopentanone, anhydrous dimethyl sulfoxide, copper phenylpropyne, and X-Phos ligand (molar ratio of 4-ethynyl-4-(4-chlorophenyl)-1,3-dioxa-2-cyclopentanone, copper phenylpropyne, and X-Phos ligand is 200:1:1) synthesized in the previous step were added to the reaction tube in the following ratio: The system was then stirred at 50°C for 24 h. The reaction formula is shown below:

[0169]

[0170] After the reaction was completed, the reaction system was extracted with tetrahydrofuran and dried, and then purified by precipitation in n-pentane to obtain a crude polymer sample. The crude sample was redissolved again with a small amount of THF and purified by precipitation and filtration in n-pentane (this operation was repeated several times) to obtain the polymer (poly(2,7-di(4-chlorophenyl)-1,8-dihydroxy-2,3,4,5,6-octapene)).

[0171] The obtained polymer was subjected to gel permeation chromatography and nuclear magnetic resonance, and the results are as follows: Figure 11 and Figure 12 As shown. Among them, Figure 11 This is a size exclusion-gel permeation chromatogram of the polymer. The horizontal axis represents retention time, which is inversely proportional to molecular weight according to the standard polystyrene calibration curve. The vertical axis represents the refractive index factor, which is directly proportional to the number of polymer molecules. Figure 12 The graph shows the 1H-NMR spectrum of the polymer. The horizontal axis represents the chemical shift, the vertical axis represents the absorption intensity, and the integrated area under the peak represents the number of active hydrogen atoms.

[0172] Example 5

[0173] This embodiment provides a polymer having the following chemical structure:

[0174] Where n is 20-22.

[0175] The method for preparing the above polymer includes the following steps:

[0176] S1: Under N2 protection, α-hydroxy-4-phenylpropanone was added to the reactor according to the feed ratio, followed by anhydrous tetrahydrofuran. A tetrahydrofuran solution of ethynyl magnesium bromide was then added under ice bath conditions. After the feed was complete, the mixture was stirred for 12 hours (the molar ratio of α-hydroxy-4-phenylpropanone to ethynyl magnesium bromide was 1:2). The mixture was quenched with saturated ammonium chloride solution and extracted with ethyl acetate. After drying, the solvent was removed under reduced pressure. The crude product, 2-(4-biphenyl)-but-3-yne-1,2-diol, was used directly in the next reaction without further treatment.

[0177] S2: Carbonyl diimidazole, 4-dimethylaminopyridine, and triethylamine were dissolved in tetrahydrofuran at the feed ratio. The crude product 2-(4-biphenyl)-but-3-yne-1,2-diol obtained in the previous step was added under stirring at room temperature and reacted for 5 h (the molar ratio of 2-(4-biphenyl)-but-3-yne-1,2-diol, carbonyl diimidazole, 4-dimethylaminopyridine, and triethylamine was 10:10:1:30). After washing the imidazole with citric acid aqueous solution, the mixture was extracted three times with dichloromethane. The organic phase was dried over anhydrous sodium sulfate, filtered to remove the solvent, concentrated under reduced pressure, and the product was purified by column chromatography to obtain 4-ethynyl-4-(4-biphenyl)-1,3-dioxa-2-cyclopentanone.

[0178] The prepared 4-ethynyl-4-(4-biphenyl)-1,3-dioxa-2-cyclopentanone was subjected to NMR, and the results are as follows: Figure 13 As shown. Figure 13 The image shows the 1H-NMR spectrum of 4-ethynyl-4-(4-biphenyl)-1,3-dioxa-2-cyclopentanone. The horizontal axis represents the chemical shift, the vertical axis represents the absorption intensity, and the integrated area under the peak represents the number of active hydrogens.

[0179] S3: Under nitrogen protection, 4-ethynyl-4-(4-biphenyl)-1,3-dioxa-2-cyclopentanone, anhydrous dimethyl sulfoxide, copper phenylpropyne, and X-Phos ligand (molar ratio of 4-ethynyl-4-(4-biphenyl)-1,3-dioxa-2-cyclopentanone, copper phenylpropyne, and X-Phos ligand is 200:1:1) synthesized in the previous step were added to the reaction tube in the following ratio: The system was then stirred at 50°C for 24 h. The reaction formula is shown below:

[0180]

[0181] After the reaction was completed, the reaction system was extracted with tetrahydrofuran and dried, and then purified by precipitation in n-pentane to obtain a crude polymer sample. The crude sample was redissolved again with a small amount of THF and purified by precipitation and filtration in n-pentane (this operation was repeated several times) to obtain the polymer (poly(2,7-di(4-biphenyl)-1,8-dihydroxy-2,3,4,5,6-octapene)).

[0182] The obtained polymer was subjected to gel permeation chromatography and nuclear magnetic resonance, and the results are as follows: Figure 14 and Figure 15 As shown. Among them, Figure 14 This is a size exclusion-gel permeation chromatogram of the polymer. The horizontal axis represents retention time, which is inversely proportional to molecular weight according to the standard polystyrene calibration curve. The vertical axis represents the refractive index factor, which is directly proportional to the number of polymer molecules. Figure 15The graph shows the 1H-NMR spectrum of the polymer. The horizontal axis represents the chemical shift, the vertical axis represents the absorption intensity, and the integrated area under the peak represents the number of active hydrogen atoms.

[0183] Examples 6-9

[0184] Examples 6-9 provide a modified polyurethane elastomer, using the polymer obtained in Example 1 as the crosslinking agent. The specific raw materials are shown in Table 1.

[0185] Table 1

[0186]

[0187] Where a: mass fraction %, b: mole fraction (in terms of the number of functional groups), and the amount of catalyst (dibutyltin dilaurate) is the percentage of the mass of the catalyst relative to the total mass of the diisocyanate, diol and modified crosslinking agent.

[0188] Embodiments 6-9 also provide a method for preparing the above-mentioned modified polyurethane elastomer, wherein the materials are fed according to the feeding ratio in Table 1, and the reaction is carried out in tetrahydrofuran at 25°C for 18 hours to obtain a gel-like elastomer. After removing the solvent under vacuum, modified polyurethane elastomers containing different modified crosslinking agents are obtained.

[0189] Examples 10-13

[0190] Examples 10-13 all provide a modified polyurethane elastomer, using the polymers obtained in Examples 2-5 as the crosslinking agent, respectively. The specific raw materials are shown in Table 2.

[0191] Table 2

[0192]

[0193] Where a: mass fraction %, b: mole fraction (in terms of the number of functional groups); the amount of catalyst (dibutyltin dilaurate) is the percentage of the mass of the catalyst relative to the total mass of the diisocyanate, diol and modified crosslinking agent.

[0194] The preparation methods of the modified polyurethane elastomers described in Examples 10-13 are the same as those in Examples 6-9, and will not be repeated here.

[0195] Comparative Example 1

[0196] This comparative example provides a modified elastomer using poly(phenyl-1,4-bis(1-hydroxy-prop-2-yne-1,3-ethylenedimethylbenzene)) as a crosslinking agent (the specific structure is shown below), and includes the following steps:

[0197] Where n is 10-13.

[0198] S1: Under N2 protection, 1,4-terephthalaldehyde was added to the reactor according to the feed ratio, followed by anhydrous tetrahydrofuran. A tetrahydrofuran solution of acetylenyl magnesium bromide was then added under ice bath conditions. After the feed was complete, the mixture was stirred for 12 hours (the molar ratio of 1,4-terephthalaldehyde to acetylenyl magnesium bromide was 1:3). The mixture was quenched with saturated ammonium chloride aqueous solution and extracted with ethyl acetate. The organic phase was dried with anhydrous sodium sulfate, filtered to remove the solvent under reduced pressure, and the product was purified by column chromatography to obtain 1,1'-(1,4-phenylene)bis(prop-2-yn-1-ol).

[0199] NMR detection of 1,1'-(1,4-phenylene)bis(prop-2-yn-1-ol) was performed, specifically as follows: Figure 16 As shown. 1H NMR (400MHz, CD3OD): δ=2.99(s,J=2.3Hz,2H), 5.40(d,J=2.3Hz,2H), 7.53(s,4H).

[0200] S2: 1,1'-(1,4-phenylene)bis(prop-2-yn-1-ol) was added to the reactor according to the feed ratio, followed by the addition of copper bromide and N,N,N',N'-tetramethylethylenediamine (the molar ratio of 1,1'-(1,4-phenylene)bis(prop-2-yn-1-ol), copper bromide, and N,N,N',N'-tetramethylethylenediamine was 5:1:20). After the feed was complete, anhydrous dichloromethane was added, and an oxygen source was connected. The mixture was stirred at room temperature for 24 hours. The mixture was quenched with a saturated ammonium chloride aqueous solution and extracted with dichloromethane. The organic phase was washed with a saturated sodium chloride solution and dried over magnesium sulfate to obtain poly(phenyl-1,4-bis(1-hydroxy-prop-2-yn-1,3-ethylenediol)), which could be used for the next step of synthesizing modified elastomers without further purification.

[0201] S3: Modified polyurethane elastomers were prepared using poly(phenyl-1,4-bis(1-hydroxy-prop-2-yne-1,3-ethylenedimethylbenzene)) obtained in S2 as a crosslinking agent. The specific raw materials are shown in Table 3.

[0202] Table 3

[0203]

[0204] Where a: mass fraction %, b: mole fraction (in terms of the number of functional groups); the amount of catalyst (dibutyltin dilaurate) is the percentage of the mass of the catalyst relative to the total mass of the diisocyanate, diol and modified crosslinking agent.

[0205] Comparative Example 1 also provides a method for preparing the above-mentioned modified elastomer. The materials are fed according to the feeding ratio in Table 3, and the reaction is carried out in tetrahydrofuran at 25°C for 18 hours to obtain a gel-like elastomer. After removing the solvent under vacuum, a modified polyurethane elastomer containing a rigid skeleton modified crosslinking agent is obtained.

[0206] Test case

[0207] The damage self-healing and self-reinforcing properties of the modified polyurethane elastomers provided in Examples 6-13 were tested, and the specific test methods are as follows:

[0208] The modified polyurethane elastomer sample was cut open, and a pressure of 300 kPa was applied to the fracture surface at 60°C for 30 seconds. A schematic diagram of the test method is shown below. Figure 17 As shown, Figure 17 The modified polyurethane elastomer used in this study is the modified polyurethane elastomer provided in Example 6.

[0209] After the above tests, it was found that the cuts of the modified polyurethane elastomers in all embodiments of the present invention, including Example 6, had healed, and all showed significant damage self-repair function.

[0210] Taking Examples 6-9 as examples, uniaxial stress tests were conducted on the modified polyurethane elastomers obtained in Examples 6-9 before and after self-healing. The results are as follows: Figure 18-21 As shown. (Through) Figure 18-21 It can be seen that the stress curve rises significantly after the yield point, with the maximum stress increasing by about 10% to 40%, while the Young's modulus at the initial transient state remains basically unchanged. Similarly, tests on Examples 10-13 also showed the same trend. This self-healing and self-reinforcing function is attributed to the secondary crosslinking process initiated in the solid phase of the crosslinked polyurethane modifier and at the notch interface. This process can be considered as the secondary crosslinking that occurs after the initial crosslinking points are activated by macroscopic stress.

[0211] Repeated strain-strain release cycle tests were performed on the elastomers obtained in Example 6 and Comparative Example 1, and the results are as follows: Figure 22 and Figure 23 As shown, the horizontal axis represents strain and the vertical axis represents stress. Figure 22 This is a cyclic uniaxial stress-strain test diagram showing the self-reinforcing function of the modified polyurethane elastomer in Example 6. Figure 23 The figure shows the cyclic uniaxial stress-strain test results for the self-reinforcing function of the modified polyurethane elastomer in Comparative Example 1. As can be seen from the figure, the modified polyurethane elastomer in Example 6 exhibits mechanical strength that increases with the number of strain (cycles), while Comparative Example 1 in cycles 1, 2, 3 and 4 (i.e., cycles 1-4) does not exhibit these properties, and its mechanical strength remains essentially unchanged with the number of strain cycles.

[0212] Therefore, the modified polyurethane elastomer of this application embodiment exhibits mechanical strength that increases with the number of strain cycles, and also shows a significant self-reinforcing function.

[0213] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A polymer, characterized in that, The polymer has the structural formula shown in formula (1): （1）； Where R is selected from any one of hydrogen, hydrocarbon, alkoxy or halogen, and n represents the degree of polymerization.

2. The polymer according to claim 1, characterized in that, In formula (1), R is selected from any one of hydrogen, alkyl, alkoxy, phenyl or halogen, and n is any integer between 20 and 30.

3. The polymer according to claim 2, characterized in that, In formula (1), R is selected from any one of hydrogen, methyl, methoxy, phenyl or chlorine, and n is any integer between 20 and 30.

4. A method for preparing the polymer according to any one of claims 1-3, characterized in that, Includes the following steps: The polymer was obtained by reacting 4-ethynyl-4-aryl-1,3-dioxa-2-cyclopentanone, a copper reagent, and an organophosphine ligand in a solvent.

5. The preparation method according to claim 4, characterized in that, The molar ratio of 4-ethynyl-4-aryl-1,3-dioxa-2-cyclopentanone, copper reagent, and organophosphine ligand is (100-200):1:1; And / or, the copper reagent includes copper acetylenicide and / or copper salts; And / or, the organophosphine ligand comprises at least one of 2-bicyclohexylphosphine-2',4',6'-triisopropylbiphenyl, triphenylphosphine, tri-n-butylphosphine, tricyclohexylphosphine, 1,2-(diphenylphosphine)ethane, or 1,3-(diphenylphosphine)propane.

6. The preparation method according to claim 5, characterized in that, The copper acetylide includes at least one of copper phenylpropyne, copper 4-trifluoromethylphenylpropyne, or copper 4-methoxyphenylpropyne.

7. The preparation method according to claim 5, characterized in that, The copper salt includes at least one of copper tetraacetonitrile hexafluorophosphate, cuprous iodide, cuprous bromide, cuprous chloride, or cuprous cyanide.

8. The preparation method according to any one of claims 4-7, characterized in that, The reaction is carried out at a temperature of 40-60℃ for 24-48 hours. And / or, the solvent for the reaction includes anhydrous dimethyl sulfoxide; And / or, after the reaction, a purification step is also included to obtain the polymer.

9. A modified crosslinking agent, characterized in that, The modified crosslinking agent includes the polymer according to any one of claims 1-3 or the polymer prepared by any one of claims 4-8.

10. A modified polyurethane elastomer, characterized in that, The modified polyurethane elastomer is mainly prepared from the following raw materials: Diisocyanate, glycol, modified crosslinking agent and catalyst; The modified crosslinking agent is the modified crosslinking agent according to claim 9.

11. The modified polyurethane elastomer according to claim 10, characterized in that, The mass ratio of the diisocyanate, diol, modified crosslinking agent, and catalyst is (6-15):(81-93):(0.5-4):5; And / or, the diol includes long-chain diols and short-chain diols; The long-chain diol includes at least one of polytetramethylene ether diol, polyethylene glycol, or polycaprolactone diol; The short-chain diol includes at least one of butanediol and pentanediol; And / or, the diisocyanate comprises at least one of 4,4'-diisocyanate diphenylmethane, 1,4-phenyl diisocyanate, toluene-2,4-diisocyanate or 1,2-phenyl diisocyanate; And / or, the catalyst comprises at least one of dibutyltin dilaurate, a tertiary amine, an organozinc reagent, or an organobismuth reagent; The tertiary amine includes 1,4-diazabicyclo[2,2,2]octene; The organic zinc reagent includes zinc diethyldithiocarbamate; The organic bismuth reagent includes at least one of bismuth trioctanoate and bismuth neodecanoate.

12. A method for preparing the modified polyurethane elastomer according to claim 10 or 11, characterized in that, Includes the following steps: A modified polyurethane elastomer is obtained by crosslinking a diol, a diisocyanate, and a modified crosslinking agent under the catalysis of a catalyst.

13. The preparation method according to claim 12, characterized in that, The temperature for the crosslinking reaction is 20-30℃; And / or, the crosslinking reaction takes 12-24 hours.

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