CN113527545B

CN113527545B - Beta-cyclodextrin polyrotaxane with accurate insertion amount, preparation method and application thereof

Info

Publication number: CN113527545B
Application number: CN202110955967.5A
Authority: CN
Inventors: 冯增国; 宋荣昊
Original assignee: Beijing Institute of Technology BIT
Current assignee: Beijing Institute of Technology BIT
Priority date: 2021-08-19
Filing date: 2021-08-19
Publication date: 2022-05-17
Anticipated expiration: 2041-08-19
Also published as: CN113527545A

Abstract

The invention relates to beta-cyclodextrin polyrotaxane with accurate insertion amount, a preparation method and application thereof, belonging to the technical field of supramolecular polymers. The beta-cyclodextrin polyrotaxane takes water-soluble polymer diamine containing an object small molecule inclusion site structure in the middle position of a molecular chain as a shaft polymer, beta-CD as a main body molecule embedded on the shaft polymer in a penetrating way, and two ends of the shaft polymer are blocked by a substance with the molecular volume larger than the size of a beta-CD cavity to form a mechanical interlocking structure. The method takes beta-CD inclusion acceptor micromolecules as preset inclusion sites, introduces water-soluble polymer diamine chain segments on two sides of the beta-CD through chemical reaction, carries out self-assembly inclusion with the beta-CD, and finally introduces large-volume end capping groups or molecules to two ends of the included polymer chains in a proper solvent by utilizing the inclusion stability between the beta-CD and the preset inclusion sites. The beta-cyclodextrin polyrotaxane can be used as a polyhydroxy crosslinking agent for damping toughening of high polymer materials.

Description

Beta-cyclodextrin polyrotaxane with accurate insertion amount, preparation method and application thereof

Technical Field

The invention relates to beta-cyclodextrin polyrotaxane with accurate insertion amount, a preparation method and application thereof, belonging to the technical field of supramolecular polymers.

Background

Cyclodextrins (CD) are polysaccharide macrocyclic molecules, typically formed from 6, 7 and 8 glucopyranose units joined end-to-end by α -1, 4-glycosidic linkages to form α -CD, β -CD and γ -CD. The unique internal hydrophobic and external hydrophilic cavity structure endows CD with the capability of forming a host-guest inclusion complex with small molecules with the size matched with the cavity size through supermolecular interaction, and also forming poly-pseudorotaxane (CD-PPR) with a polymer through self-assembly. The structural parameters of CD and the common guest small molecules and polymers capable of self-assembly inclusion with CD are shown in table 1.

TABLE 1

Cyclodextrin polyrotaxane (CD-PR) is prepared by penetrating CD onto a guest polymer chain to form CD-PPR, and then performing end capping reaction, namely, connecting bulky groups or molecules to two ends of the wrapped polymer chain by using chemical reaction to form a mechanical interlocking structure. The CD-PR is used for changing the capability of CD to move along a molecular chain at the cost of sacrificing the host-guest inclusion capability of CD and guest molecules, namely the CD can generate synergistic molecular motion with a penetrated and embedded polymer chain and also can generate relative sliding and rotation on the polymer chain so as to make multistage response to external stimuli and generate adaptive change.

Compared with polyrotaxane based on other macrocyclic molecules, such as crown ether, cucurbituril, calixarene, pillararene, various cycloparaffins and the like, the CD component in the CD-PR is obtained by degrading amylase, and the method has the advantages of wide raw material source, biodegradability, environment-friendly production process and sustainable development. Meanwhile, 18, 21 and 24 hydroxyl groups are respectively contained outside the cavities of the alpha-CD, the beta-CD and the gamma-CD, which provides convenience for the subsequent chemical modification and performance improvement of the CD-PR. In addition, in the CD-PR formed by the mechanical interlocking structure, no covalent bond connection exists between the CD of the chain-through-embedded chain and the main polymer chain, and the decomposition and the damage of the CD-PR can be caused only by the breakage of a large ring or the breakage of the polymer chain. Therefore, compared with the supermolecule polymer formed by non-covalent bond interaction such as hydrogen bond, van der waals force, dipole-dipole effect, hydrophilic and hydrophobic interaction and the like, the CD-PR has the same chemical stability and physical and mechanical properties as the polymer formed by covalent bond connection, and can be used for or replacing the traditional load-bearing engineering polymer material and also can be used for an emerging intelligent high molecular material. Applications of CD-PR include: the compound can be directly used as a Niemann-Peak C type metabolic disease treatment drug (D.H.Thompson et al US 2021040270A1), a bacteriostatic and antibacterial material capable of releasing nitric oxide (Malan et al CN110527108A), a scratch-proof self-healing mobile phone screen, an automobile coating, optical glass (Y.Noda et al J.appl.Polymer.Sci, 2014,40509; H-J.Sue et al WO2021039942A1), a large deformation wearable electronic device (R.Du et al adv.Funct.Mater, 2019, 30,1907139), a rechargeable lithium ion battery silicon cathode high elongation adhesive (S.Choi et al Science,2017,357, 279-283), a chemically synthesized and natural polymer reinforcing material toughening agent (Wanjin Yuan et al CN109021328A), a crack-proof oilfield concrete material (H.A.Patel et al US2021130676A1) and the like.

However, in the above applications, such as CD-PR formed by self-assembly of beta-CD as a therapeutic agent for Niemann-Pick C type metabolic disease and PEG-PPG-PEG triblock copolymer after encapsulation (D.H.Thompson et al, US 2021040270A1), CD-PR formed by encapsulation of alpha-CD of optical glass and PEG after encapsulation (Y.Noda et al, J.Appl.Polym.Sci.,2014,40509; H-J.Sue et al, WO2021039942A1), and CD-PR formed by encapsulation of gamma-CD of concrete material for crack prevention oil field and PDMS after encapsulation (H.A.Patel et al, US2021130676A1), all of which are not always formed by self-assembly under the drive of non-interaction such as hydrogen bond, van der Waals force, dipole-dipole covalent bond and hydrophobic interaction when the cross-sectional area of the selected polymer matches the size of the CD cavity, then carrying out end capping reaction. Since these polymers have uniform chain structure and lack definite and efficient inclusion sites and groups, the product yield and repeatability are severely reduced only by changing self-assembly inclusion conditions such as charge ratio, polymer molecular weight, inclusion temperature and time, if excessive CD penetrates through the embedded chain and then is densely arranged to form pipeline crystallization, or if only a small amount of CD penetrates through the embedded chain, thus (Y.Kobayashi et al chem.Commun.,2018,54, 7066-7069). To achieve accurate control of the number of uplink CDs, both in CD-PR synthesis methods and in application research, is fraught with significant challenges.

When the slip ring structure of the CD-PR is used as an energy dissipation element for preparing the damping toughening material, accurate control of the quantity of the uplink CD is particularly important, because a large number of CDs which cannot participate in chain extension and crosslinking reactions occupy a polymer chain, the movement space of the CDs after chain extension and crosslinking is limited, the solubility of a pipeline crystal structure formed by densely arranged CDs is reduced, the subsequent processing difficulty of a solvent and melting is increased, the compatibility with the damping toughening matrix material is changed, and the mechanical property is extremely adversely affected (Y.Kobayashi Polymer.J., 2021,53: 505-. In addition, the overbretched CDs also increase the molecular weight of the overall energy dissipation element, causing an increase in the mass fraction of the overall element in the matrix material, leading to increased product costs. It can be seen that to maximize the function of the CD-PR slip ring structure as an energy dissipation element, the CD insertion amount should be controlled to be the minimum insertion amount of 2.

How to control the CD insertion amount to 2. As shown in table 1, the lumen size of β -CD is between α -CD and γ -CD.The cross-sectional area adaptive PPR can be formed by self-assembling and coating polymer chains (such as PPG and the like) with adaptive cross-sectional areas, CD-PR is obtained after end sealing, various organic small molecules with proper sizes can be coated, such as ferrocene, adamantane, cholesterol, azobenzene and the like, an inclusion compound with a determined inclusion ratio is formed by host-guest inclusion, and the inclusion constant is as high as 10³～10⁴M^-1(F.Hapiot et al chem.Rev.,2006,106, 767-781).

However, the current methods for controlling the amount of cyclodextrin insertion in Polyrotaxane (PR) are only found in the research work of self-assembly inclusion of alpha-CD and diamine containing 10 or 12 carbon chains, and then capping reaction to obtain an adapted primary alpha-CD 3 PR (Y. Akae et al Angew. chem. int. Ed.2018,57, 1-6). In order to obtain larger movement space for the alpha-CD of the embedded chain, the method also needs to carry out chemical modification on the end-capping group, and then carry out end capping after the main chain is extended through reactions such as free radical polymerization or ring-opening polymerization. Because of the long reaction route, the final alpha-CD 3 PR yield is low, and at present, the route does not draw attention. The inclusion of the existing beta-CD and ferrocene and other substances is mostly limited in the small molecular category or the polymer side group modification field, and the beta-CD is proved to be difficult to form a stable PR structure with PEG and other polymers due to the difference of the cavity suitability.

Disclosure of Invention

In view of the above, the present invention is to provide a beta-cyclodextrin polyrotaxane (beta-CD 3 PR) with accurate insertion amount, a preparation method and applications thereof. The beta-CD insertion number in the beta-cyclodextrin polyrotaxane is 2, and the beta-cyclodextrin polyrotaxane has good stability. The method uses object small molecule of inclusion beta-CD as preset inclusion site, introduces water soluble polymer diamine chain segment on two sides through chemical reaction, then self-assembles with beta-CD in water to form beta-CD-PPR, finally introduces large volume end capping group or molecule to two ends of the included polymer chain in proper solvent by using inclusion stability between beta-CD and preset inclusion site, and obtains beta-CD 3 PR. Because of the existence of intramolecular frictional resistance, the slip ring structure in beta-CD 3 PR can slide and rotate along the wrapped polymer chain under the action of external force, so as to balance and disperse external stress, and can play the role of energy dissipation element, and can be used as polyhydroxy crosslinking agent for damping toughening high-molecular material.

In order to achieve the purpose, the technical scheme of the invention is as follows:

beta-cyclodextrin polyrotaxane (beta-CD 3 PR) with accurate insertion amount, wherein the beta-cyclodextrin polyrotaxane takes water-soluble polymer diamine containing a guest micromolecule inclusion site structure at the middle position of a molecular chain as an axial polymer, beta-CD as a host molecule inserted on the axial polymer, and two ends of the axial polymer are blocked by a substance with the molecular volume larger than the cavity size of the beta-CD to form a mechanical interlocking structure; wherein the insertion amount of the beta-CD is 2, the guest micromolecule is an inclusion micromolecule substance of the beta-CD, the water-soluble polymer diamine is a linear polymer with both ends modified by amino and the molecular sectional area smaller than the cavity size of the beta-CD, and the guest micromolecule is connected with the water-soluble polymer diamine through an amide bond.

Preferably, the guest small molecule is ferrocene, adamantane or azobenzene.

Preferably, the water-soluble polymer diamine is a polyether diamine or a polyester diamine. More preferably, the polyether diamine is polyethylene glycol diamine, polytetrahydrofuran ether diamine, ethylene oxide/propylene oxide copolyether diamine, or ethylene oxide/tetrahydrofuran copolyether diamine; the polyester diamine is polyethylene glycol succinate diamine, polybutylene succinate diamine or polyhexamethylene glycol succinate diamine. Most preferably, the molecular weight of the water-soluble polymer diamine is 500-4000.

A method for preparing the beta-cyclodextrin polyrotaxane (beta-CD 3 PR) with accurate intercalation amount comprises the following steps:

(1) adding a guest micromolecule derivative, water-soluble polymer diamine, a catalyst I for amide condensation, an acid-binding agent I for amide condensation and a solvent I into a reaction container, stirring for 24-48 h at 25-35 ℃ to obtain a solution, concentrating the solution, and dialyzing in water with the purity higher than that of deionized water for 8-10 h to obtain a shaft polymer solution which contains a preset inclusion site and has amino groups at the end groups on two sides; wherein the guest micromolecule derivative is a substance which is wrapped by beta-CD and contains carboxyl at two ends of micromolecule;

(2) adding the shaft polymer solution and beta-CD into water with the purity higher than that of deionized water at the temperature of 25-45 ℃, mixing and stirring for 4-5 days, and drying to obtain beta-cyclodextrin poly-pseudorotaxane (beta-CD-PPR);

(3) adding the beta-CD-PPR, end-capping reagent, catalyst II for amide condensation, acid-binding agent II for amide condensation and solvent II into a reaction container, stirring at 25-35 deg.C for 24-48 h to obtain suspension, performing solid-liquid separation on the suspension, washing the solid, dissolving in dimethyl sulfoxide (DMSO), dialyzing in water with the purity of deionized water for 4-6 days, and drying to obtain beta-cyclodextrin polyrotaxane (beta-CD 3 PR) with accurate insertion amount; wherein the solvent II can not dissolve the beta-CD-PPR but can dissolve the end-capping agent, the catalyst II for amide condensation and the acid-binding agent II for amide condensation.

In the step (1):

preferably, the guest small molecule derivative is ferrocene dicarboxylic acid, adamantane dicarboxylic acid or azobenzene dicarboxylic acid.

Preferably, the water-soluble polymer diamine is a polyether diamine or a polyester diamine. More preferably, the water-soluble polymer diamine is polyethylene glycol diamine, polytetrahydrofuran ether diamine, ethylene oxide/propylene oxide copolyether diamine, ethylene oxide/tetrahydrofuran copolyether diamine, polyethylene glycol succinate diamine, polybutylene succinate diamine, or polyhexamethylene glycol succinate diamine. Most preferably, the molecular weight of the water-soluble polymer diamine is 500-4000.

Preferably, the catalyst I for amide condensation is benzotriazol-1-yl-oxytripyrrolidinophosphonium hexafluorophosphate (PyBOP).

Preferably, the acid-binding agent I for amide condensation is N, N-diisopropylethylamine or triethylamine.

Preferably, the solvent I is N, N-Dimethylformamide (DMF).

Preferably, the molar ratio of the guest small molecule derivative, the water-soluble polymer diamine, the catalyst I for amide condensation and the acid-binding agent I for amide condensation is 1: 3.3-4.4: 2.1-2.8, and the molar ratio of the catalyst I for amide condensation and the acid-binding agent I for amide condensation is 1: 1.

Preferably, the mass ratio of the solvent I to the guest small molecules is 50: 1-80: 1.

Preferably, a dialysis bag with the molecular weight cut-off of 0.8 to 1.2 times of the molecular weight of the water-soluble polymer diamine is adopted during dialysis.

In the step (2):

preferably, the molar ratio of the axial polymer to the beta-CD in the axial polymer solution is greater than or equal to 1: 2. More preferably, the molar ratio of the axial polymer to the beta-CD is 1:2 to 1: 20.

Preferably, the mass ratio of the water to the beta-CD is 50: 1-100: 1. The formation of the beta-CD-PPR structure is further ensured by controlling the feed ratio of water to beta-CD in order to reduce as much as possible the competition between the beta-CD self-aggregation and the intercalation process on the axial polymer.

In the step (3):

preferably, the blocking agent is one or more of carboxytriphenylmethane, carboxytetraphenylmethane and tritylglycine.

Preferably, the catalyst II for amide condensation is benzotriazole-1-yloxytris (dimethylamino) phosphonium hexafluorophosphate (BOP).

Preferably, the acid-binding agent II for amide condensation is N, N-diisopropylethylamine.

Preferably, the solvent II is Tetrahydrofuran (THF) and acetonitrile (CH)₃CN) was added to the solvent.

Preferably, the molar ratio of the beta-CD-PPR to the end-capping reagent to the catalyst II for amide condensation to the acid-binding agent II for amide condensation is 1: 8-10: 8.2-10.5, and the molar ratio of the catalyst II for amide condensation to the acid-binding agent II for amide condensation is 1: 1.

Preferably, the mass ratio of the beta-CD-PPR to the solvent II is 15: 1-20: 1.

Preferably, Tetrahydrofuran (THF) and acetonitrile (CH) are used for washing₃CN)、One or more of acetone and methanol.

Preferably, a dialysis bag with the molecular weight cut-off of 1.5 to 2.5 times of the molecular weight of the water-soluble polymer diamine is adopted during dialysis.

The application of beta-cyclodextrin polyrotaxane (beta-CD 3 PR) with accurate penetrating amount as cross-linking agent in preparing damping toughened polymer material.

Preferably, the beta-cyclodextrin polyrotaxane is used as a cross-linking agent in the preparation of the reticular structure polyurethane cross-linked elastomer, and the preparation method comprises the following steps:

(1) dissolving the polymer diol in dry solvent III, adding diisocyanate, and dissolving in N₂Stirring for 6-8 h at 55-65 ℃ under protection to obtain a prepolymer solution;

(2) dissolving beta-cyclodextrin polyrotaxane (beta-CD 3 PR) and curing catalyst in dry solvent IV, removing bubbles at 25-35 deg.C and vacuum degree less than or equal to-0.04 MPa for 10-30 min, adding into the prepolymer solution, stirring at 25-35 deg.C for 10-15 min, pouring into mould, continuously curing at 50-60 deg.C for more than 48 hr, cooling and demoulding to obtain the invented product.

In the step (1):

preferably, the polymer diol is one or more of polyether diol, polyester diol and polycarbonate diol. More preferably, the polymer diol is at least one selected from the group consisting of polyethylene glycol (PEG), polypropylene glycol (PPG), Polytetrahydrofuran (PTHF), ethylene oxide/propylene oxide copolyether, ethylene oxide/tetrahydrofuran copolyether diol, polyethylene succinate, polybutylene succinate diol, poly 1, 4-butanediol carbonate diol, and poly 1, 6-hexanediol carbonate diol. Most preferably, the polymer diol has a functionality of 1.85 to 2.15 and a number average molecular weight of 2000 to 10000.

Preferably, the diisocyanate is one or more of 4,4 '-dicyclohexylmethane diisocyanate (HMDI), isophorone diisocyanate (IPDI), Hexamethylene Diisocyanate (HDI), L-lysine ethyl ester diisocyanate (LDI), tetramethylene diisocyanate (BDI), diphenylmethane-4, 4' -diisocyanate (MDI) and 2, 4-Toluene Diisocyanate (TDI).

Preferably, the curing catalyst is one or more of an organotin catalyst and an organic base catalyst. More preferably, the curing catalyst is one or more of dibutyltin dilaurate (T-12), stannous octoate, triethylamine, 1, 4-diazabicyclo [2.2.2] octane (DABCO), bis-dimethylaminoethyl ether and 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU).

Preferably, the solvent III and the solvent IV are respectively and independently one or more of dimethyl sulfoxide (DMSO), N-Dimethylformamide (DMF), dimethylacetamide and N-methylpyrrolidone.

Preferably, the diisocyanate is 2.05 to 2.15 times the molar amount of the polymer diol, and the molar ratio of the cyclodextrin polyrotaxane to the polymer diol is 0.3:1 or more. More preferably, the molar ratio of the cyclodextrin polyrotaxane to the polymer diol is 0.3:1 to 0.6: 1. More preferably, the molar ratio of the cyclodextrin polyrotaxane to the polymer diol is 0.4:1 to 0.5: 1.

Preferably, the mass of the curing catalyst is 0.5-0.8% of the total mass of the cyclodextrin polyrotaxane and the polymer diol.

Advantageous effects

The beta-cyclodextrin polyrotaxane (beta-CD 3 PR) with accurate insertion amount has good stability, the beta-CD can not slip from a shaft polymer when being dissolved in a high-boiling-point organic solvent (such as DMF and DMSO), and thermal degradation behavior does not exist below 200 ℃. beta-CD 3 PR is biocompatible and easy to degrade, and belongs to a material with sustainable development and environmental friendliness.

In the preparation process of the method, the structural types of the shaft polymer in the PR structure are enriched. Through the selective inclusion behavior of the beta-CD at the inclusion site in the axial polymer and the cleaning effect of the heterogeneous end capping process on the non-adaptive inclusion, the accurate control of the insertion amount of the beta-CD in the PR is realized, and the movement space of the beta-CD on the included polymer chain is ensured. Meanwhile, in the steps of insertion and end capping, the hydroxyl on the beta-CD does not participate in chemical reaction, and the polyhydroxy structure of the beta-CD is reserved after the beta-CD 3 PR is formed, so that various chemical modifications and performance modifications are allowed to be carried out subsequently.

Furthermore, the method can more accurately control the beta-CD intercalation amount by selecting each reactant and controlling the adding amount of each substance in the reaction process. And the selected material has wide source selection range, low price and easy obtainment.

beta-CD [3] of the invention]PR is used as a cross-linking agent, and can fully play the damping and toughening functions of the energy dissipation elements. Further, the beta-CD [3] is subjected to]PR is used as cross-linking agent in preparing cross-linked netted polyurethane elastomer and is prepared from beta-CD 3]Maximum breaking stress (sigma) of a polyurethane crosslinked elastomer obtained by PR (positive resist) curing crosslinking measured in a tensile test_m) The elongation (epsilon) under the maximum strength is improved by 30 to 65 percent_m) Increase the fracture energy (G) by 60 to 160 percent_F) The improvement is 90 to 226 percent. In the range of 30-100 ℃, the material has lower elastic modulus and higher loss angle in dynamic thermomechanical analysis (DMA) test.

Drawings

FIG. 1 is a nuclear magnetic hydrogen spectrum of β -CD, axial polymer and β -CD 3 PR as described in example 1.

FIG. 2 is an infrared spectrum of PEG1000 diamine, axial polymer and beta-CD 3 PR as described in example 1.

FIG. 3 is a gel permeation chromatogram of PEG1000 diamine, axial polymer, and β -CD 3 PR in DMF as described in example 1.

FIG. 4 is a thermogravimetric plot of the β -CD 3 PR described in example 1.

FIG. 5 is a wide angle X-ray diffraction (XRD) pattern of the β -CD 3 PR described in example 1.

FIG. 6 is a stress-strain curve of the polyurethane crosslinked elastomers described in comparative examples 1 to 4.

FIG. 7 is a stress-strain curve of the polyurethane crosslinked elastomers described in examples 8-11.

FIG. 8 is a stress-strain curve of the polyurethane crosslinked elastomers described in comparative examples 5 to 8.

FIG. 9 is a stress-strain curve of the polyurethane crosslinked elastomers described in examples 12-15.

FIG. 10 shows the results of the energy to break of the polyurethane crosslinked elastomers described in comparative examples 1 to 4 and examples 8 to 11.

FIG. 11 shows the results of the energy to break of the polyurethane crosslinked elastomers described in comparative examples 5 to 8 and examples 12 to 15.

FIG. 12 shows the results of dynamic mechanical property tests of the polyurethane crosslinked elastomer described in comparative example 1.

FIG. 13 shows the results of dynamic mechanical property tests of the polyurethane crosslinked elastomer described in example 8.

FIG. 14 shows the results of dynamic mechanical property tests of the polyurethane crosslinked elastomer described in comparative example 5.

FIG. 15 shows the results of dynamic mechanical property tests of the polyurethane crosslinked elastomer described in example 12.

FIG. 16 is a structural model diagram of the beta-CD 3 PR according to the present invention.

Detailed Description

The present invention will be described in further detail with reference to specific examples.

In the following examples:

(1) in examples 1 to 7, the feed ratio was in mole fraction unless otherwise specified.

(2) In examples 8 to 15 and comparative examples 1 to 4, the feed ratio was in parts by mass unless otherwise specified.

(3) In examples 1 to 7, the polymer diamine was prepared by the following method:

adding polymer glycol, N' -Carbonyldiimidazole (CDI) and Tetrahydrofuran (THF) into a reaction vessel, reacting for more than 24h at 25-35 ℃ under the protection of nitrogen, then adding excessive ethylenediamine, continuing to react for more than 24h at 25-35 ℃, re-dissolving in dichloromethane after evaporation and concentration to obtain a crude product solution; the crude product solution was washed with saturated brine, evaporated, concentrated, precipitated in glacial ethyl ether and dried to give the polymer diamine.

Preferably, the molar ratio of the polymer glycol to the CDI to the ethylenediamine is 1: 8-12: 40-60, and the mass ratio of the THF to the polymer glycol is 6-12: 1. The volume of the added dichloromethane is 1.2-1.5 times of the volume of the solution before concentration, the volume ratio of the saturated saline solution of the washing solution to the crude product solution is 1: 5-7, and the washing times are 3-5 times.

Preferably, the polymer diol is a polyether diol, a polyester diol, or a polycarbonate diol. More preferably, the polymer diol is PEG, PPG, PTHF, ethylene oxide/propylene oxide copolyether, ethylene oxide/tetrahydrofuran copolyether diol, polyethylene succinate, polybutylene succinate, polyhexamethylene succinate diol, poly 1, 4-butanediol carbonate diol, or poly 1, 6-hexanediol carbonate diol. Most preferably, the polymer diol has a functionality of 1.85 to 2.15 and a number average molecular weight of 2000 to 10000.

Example 1

A method for preparing beta-CD 3 PR comprises the following steps:

(1) 1 part of PEG1000, 8.0 parts of CDI and dry THF which is 8 times of the weight of PEG1000 are added into a reaction vessel, and the mixture is uniformly mixed under the protection of nitrogen and then reacted for 24 hours at 25 ℃. Adding 40 parts of ethylenediamine, continuously reacting for 24 hours at 25 ℃ under the protection of nitrogen, carrying out rotary evaporation and concentration on the obtained solution, adding dichloromethane which is 15 times of PEG1000 by mass, uniformly mixing, pouring into a liquid separation device, adding saturated salt water which is 0.2 times of the volume of dichloromethane, fully oscillating, washing, standing for 5min, separating out an organic phase, and repeatedly washing for 4 times. Adding 20 parts of anhydrous sodium sulfate, fully shaking, filtering after 5min, reserving a liquid phase, evaporating and concentrating, precipitating in 50 parts of glacial ethyl ether, collecting the precipitate, and drying in vacuum to obtain 0.7 part of PEG1000 diamine.

(2) Adding 0.2 part of 1,1 '-ferrocene dicarboxylic acid, 0.45 part of PyBOP, 0.45 part of N, N-diisopropylethylamine and 60 times of mass part of DMF (dimethyl formamide) equivalent to 1, 1' -ferrocene dicarboxylic acid into a reaction container, stirring for 5min, adding 0.7 part of PEG1000 diamine, stirring for 24h at 25 ℃, performing rotary evaporation and concentration on the obtained solution, adding 2 parts of deionized water, dialyzing for 9h in the deionized water by using a 1000D cellulose dialysis bag, and replacing the dialysate every 3 h. And (3) freeze-drying the dialysate to obtain 0.1 part of axial polymer containing the ferrocene preset inclusion sites.

(3) 0.1 part of the axial polymer and 0.4 part of beta-CD are mixed and stirred in deionized water with the mass part being 60 times that of the beta-CD for 5 days at 25 ℃, and the mixture is blown and dried for 24 hours at 80 ℃ to obtain the beta-CD-PPR.

(4) In a reaction vessel, 0.1 part of the beta-CD-PPR, 0.8 part of trityl glycine, 0.85 part of BOP, 0.85 part of N, N-diisopropylethylamine, THF and CH in a volume ratio of 1:1 corresponding to 15 mass parts of the beta-CD-PPR are added₃CN mixed solvent, stirring at 25 deg.C for 24h, performing solid-liquid separation, washing the solid with 1.5 parts THF for 3 times, washing with 1.5 parts acetone for 2 times, dissolving in 1 part DMSO, dialyzing with 2000D cellulose dialysis bag in deionized water for 6 days, and freeze drying to obtain 0.025 parts beta-CD 3]PR。

FIG. 1 shows the beta-CD, axial polymer and beta-CD [3] of this example]Nuclear magnetic hydrogen spectrum of PR (¹H NMR) diagram, wherein A is beta-CD, B is axial polymer, and C is beta-CD 3]PR; the results show a molar ratio of β -CD to axial polymer of 2.03: 1.

FIG. 2 shows the PEG1000 diamine, axial polymer and beta-CD 3 of this example]An infrared spectrum of PR, wherein A is PEG1000 diamine, B is axial polymer, and C is beta-CD 3]PR; the results showed that the peak density was at 3400cm^-1～3100cm^-1The presence of hydroxyl peaks was detected in the wavenumber range, which initially indicated the presence of β -CD on the axial polymer. In addition, at 1730cm^-1～1670cm^-1The presence of amide bonds was detected in the wavenumber range.

FIG. 3 is a gel permeation chromatogram of PEG1000 diamine, axial polymer and beta-CD 3 PR in DMF of this example, wherein A is PEG1000 diamine, B is axial polymer, and C is beta-CD 3 PR; the results show that no efflux peak of free β -CD was detected and that the polymer possesses a larger molecular weight than the axial polymer, demonstrating the formation of a Polyrotaxane (PR) mechanical interlock. The combined nuclear magnetic hydrogen spectrum results show that the beta-CD insertion amount in the obtained beta-CD 3 PR is 2.

FIG. 4 is a thermogravimetric plot of the beta-CD 3 PR in this example, showing that the thermal decomposition process of the beta-CD 3 PR can be divided into three stages: (1)271 ℃ -310 ℃, the interval corresponds to the decomposition of the PEG chain segment and is close to the shaft polymer; (2) decomposition of beta-CD at 310-362 deg.c; (3) the temperature range above 370 ℃ corresponds to degradation of the ferrocene moiety, indicating a structure in which the β -CD is embedded on the axial polymer in the product.

FIG. 5 is a wide angle XRD pattern of the beta-CD 3 PR of this example, showing that the characteristic diffraction peaks (at 19.8 and 23.8) for PEG in the axial polymer are not detected, confirming the coating of beta-CD on the axial polymer. The molecular weight and distribution of beta-CD 3 PR are shown in Table 2.

TABLE 2

The test result shows that the beta-CD 3 PR takes polyethylene glycol diamine containing ferrocene inclusion site structure in the middle of molecular chain as the shaft polymer, beta-CD as the main molecule embedded in the shaft polymer, and the two ends of the shaft polymer are blocked by triphenyl glycine to form a mechanical interlocking structure; the insertion amount of the beta-CD is 2, and the ferrocene and the polyethylene glycol diamine are connected through amido bond; the chemical structure is as follows:

the calculated molar yield is 25%, the beta-CD 3 PR shows a swelling state similar to gel after being soaked in water for 24 hours, and can be dissolved in DMSO and DMF.

Example 2

A method for preparing beta-CD 3 PR comprises the following steps:

(1) 1 part of PEG2000, 10.0 parts of CDI and dry THF which is 6 times of the weight of PEG2000 are added into a reaction vessel, and the mixture is uniformly mixed under the protection of nitrogen and then reacted for 24 hours at 30 ℃. Adding 50 parts of ethylenediamine, continuously reacting for 24 hours at 30 ℃ under the protection of nitrogen, performing rotary evaporation and concentration on the obtained solution, adding 17 times of PEG2000 parts by mass of dichloromethane, uniformly mixing, pouring into a liquid separation device, adding saturated salt water with the volume of 0.2 times of that of the dichloromethane, fully oscillating for washing, standing for 5min, separating out an organic phase, and repeatedly washing for 4 times. Adding 20 parts of anhydrous sodium sulfate, fully shaking, filtering after 5min, reserving a liquid phase, evaporating and concentrating, precipitating in 50 parts of glacial ethyl ether, collecting precipitate, and drying in vacuum to obtain 0.85 part of PEG2000 diamine.

(2) Adding 0.2 part of 1,1 '-ferrocene dicarboxylic acid, 0.5 part of PyBOP, 0.5 part of N, N-diisopropylethylamine and 60 times of mass part of DMF (dimethyl formamide) equivalent to 1, 1' -ferrocene dicarboxylic acid into a reaction container, stirring at normal temperature for 5min, adding 0.85 part of PEG2000 diamine, stirring at 30 ℃ for 24h, carrying out rotary evaporation concentration on the obtained solution, adding 2 parts of deionized water, dialyzing in the deionized water for 9h by using a 2000D cellulose dialysis bag, and replacing the dialyzate every 3 h. And (3) freeze-drying the dialysate to obtain 0.1 part of axial polymer containing the ferrocene preset inclusion sites.

(3) 0.1 part of the axial polymer and 0.6 part of beta-CD are mixed and stirred in deionized water with the mass part being 80 times that of the beta-CD for 5 days at the temperature of 30 ℃, and the mixture is blown and dried for 24 hours at the temperature of 80 ℃ to obtain the beta-CD-PPR.

(4) In a reaction vessel, 0.1 part of the beta-CD-PPR, 0.8 part of trityl glycine, 0.85 part of BOP, 0.85 part of N, N-diisopropylethylamine, THF and CH in a volume ratio of 1:1 corresponding to 15 mass parts of the beta-CD-PPR are added₃CN mixed solvent, stirred at 30 ℃ for 24 hours, the resulting suspension was subjected to solid-liquid separation, and the solid was washed with 1.5 parts of THF 3 times and then with 1.5 parts of CH₃CN is washed for 2 times, dissolved in 1 part of DMSO, dialyzed in deionized water for 6 days by using 3500D cellulose dialysis bag, and freeze-dried to obtain 0.03 part of beta-CD 3]PR。

The beta-CD [3]]Of PR¹The H NMR spectrum showed a molar ratio of beta-CD to axial polymer of 2.11: 1.

The beta-CD [3]]PR infrared absorption spectrum at 3400cm^-1～3100cm^-1The presence of hydroxyl peaks was detected in the wavenumber range, which initially indicated the presence of β -CD on the axial polymer. In addition, at 1730cm^-1～1670cm^-1The presence of amide bonds was detected in the wavenumber range.

The beta-CD [3]]Undetected in gel permeation chromatography of PRThe formation of PR mechanical interlocking structures is evidenced by the efflux peak of free β -CD and possessing a larger molecular weight than the axial polymer. Results¹The result of H NMR spectrum proves that the beta-CD 3]The amount of beta-CD insertion in PR was 2.

The results of thermogravimetric analysis of the beta-CD 3 PR indicate that the beta-CD in the product is embedded in the structure of the axial polymer.

The wide angle XRD results of the beta-CD 3 PR showed no detection of characteristic diffraction peaks (at 19.8 ℃ and 23.8 ℃) for PEG in the axial polymer, confirming the coating of beta-CD on the axial polymer.

The test result shows that the beta-CD 3 PR takes polyethylene glycol diamine containing ferrocene inclusion site structure in the middle of molecular chain as the shaft polymer, beta-CD as the main molecule embedded in the shaft polymer, and the two ends of the shaft polymer are blocked by triphenyl glycine to form a mechanical interlocking structure; the insertion amount of the beta-CD is 2, and the ferrocene and the polyethylene glycol diamine are connected through an amide bond.

The calculated molar yield is 32%, the beta-CD 3 PR shows a swelling state similar to gel after being soaked in water for 24 hours, and can be dissolved in DMSO and DMF.

Example 3

A method for preparing beta-CD 3 PR comprises the following steps:

(1) same as example 1, step (1).

(2) Same as example 1, step (2).

(3) 0.1 part of the axial polymer and 0.8 part of beta-CD are mixed and stirred in deionized water with the mass part being 80 times that of the beta-CD for 5 days at the temperature of 35 ℃, and the mixture is blown and dried for 24 hours at the temperature of 80 ℃ to obtain the beta-CD-PPR.

(4) In a reaction vessel, 0.1 part of the beta-CD-PPR, 0.8 part of trityl glycine, 0.85 part of BOP, 0.85 part of N, N-diisopropylethylamine, THF and CH in a volume ratio of 1:1 corresponding to 15 mass parts of the beta-CD-PPR are added₃CN mixed solvent, stirring at 25 deg.C for 24h, separating solid and liquid of the obtained suspension, washing the solid with 1.5 parts THF for 3 times, 1.5 parts acetone for 2 times, and 1.5 parts methanol for 1 time, dissolving in 1 part DMSO, and removing ions with 2000D cellulose dialysis bagDialyzing in water for 6 days, freeze drying to obtain 0.021 weight portion of beta-CD 3]PR。

The beta-CD [3]]Of PR¹The H NMR spectrum showed a molar ratio of beta-CD to axial polymer of 2.08: 1.

The beta-CD [3]]The gel permeation chromatography of PR does not detect the free β -CD efflux peak and possesses a larger molecular weight than the axial polymer, demonstrating the formation of PR mechanical interlock structures. As a result, the¹The result of H NMR spectrum proves that the beta-CD 3]The amount of beta-CD insertion in PR was 2.

The molecular weight of the beta-CD 3 PR and the distribution thereof are shown in Table 3.

TABLE 3

The test result shows that the beta-CD 3 PR takes polyethylene glycol diamine containing ferrocene inclusion site structure in the middle of molecular chain as the shaft polymer, beta-CD as the main molecule embedded in the shaft polymer, and the two ends of the shaft polymer are blocked by triphenyl glycine to form a mechanical interlocking structure; the insertion amount of the beta-CD is 2, and the ferrocene is connected with the polyethylene glycol diamine through an amide bond.

The calculated molar yield is 21%, the beta-CD 3 PR shows a swelling state similar to gel after being soaked in water for 24 hours, and can be dissolved in DMSO and DMF.

Example 4

A method for preparing beta-CD 3 PR comprises the following steps:

(1) in a reaction vessel, 1 part of Polytetrahydrofuran (PTHF)1000, 8.0 parts of CDI and 1000 parts by mass of dry THF equivalent to 9 times of PTHF were charged, mixed uniformly under nitrogen protection and reacted at 25 ℃ for 24 hours. Adding 40 parts of ethylenediamine, continuously reacting for 24 hours at 25 ℃ under the protection of nitrogen, carrying out rotary evaporation and concentration on the obtained solution, adding dichloromethane which is 18 times of PTHF in 1000 parts by weight, uniformly mixing, pouring into a liquid separating device, adding saturated salt water which is 0.2 times of dichloromethane in volume, fully oscillating for washing, standing for 5min, separating out an organic phase, and repeatedly washing for 3 times. 20 parts of anhydrous magnesium sulfate are added and sufficiently shaken, the liquid phase is filtered after 5min and retained and evaporated and concentrated, then the precipitate is precipitated in 50 parts of glacial ethyl ether, and the precipitate is collected and dried under vacuum to obtain 0.7 part of PTHF1000 diamine.

(2) Adding 0.2 part of 1,1 '-ferrocene dicarboxylic acid, 0.45 part of PyBOP, 0.45 part of N, N-diisopropylethylamine and 70 times of mass part of DMF (dimethyl formamide) equivalent to 1, 1' -ferrocene dicarboxylic acid into a reaction container, stirring at normal temperature for 5min, adding 0.7 part of PTHF1000 diamine, stirring at 25 ℃ for 24h, performing rotary evaporation concentration on the obtained solution, adding 2 parts of deionized water, dialyzing in the deionized water for 9h by using a 1000D cellulose dialysis bag, and replacing the dialysate every 3 h. And (3) freeze-drying the dialysate to obtain 0.1 part of axial polymer containing the ferrocene preset inclusion sites.

(4) In a reaction vessel, 0.1 part of the beta-CD-PPR, 0.8 part of trityl glycine, 0.85 part of BOP, 0.85 part of N, N-diisopropylethylamine, THF and CH in a volume ratio of 1:1 corresponding to 15 mass parts of the beta-CD-PPR are added₃CN mixed solvent, stirring at 25 deg.C for 24 hr, and making the obtained suspension undergo the process of solid-liquid separationThe solid is separated, washed 2 times with 1.5 parts of THF, 1.5 parts of CH₃CN washing for 2 times, washing with 1.5 parts acetone for 2 times, dissolving in 1 part DMSO, dialyzing with 2000D cellulose dialysis bag in deionized water for 6 days, and freeze drying to obtain 0.022 parts of beta-CD 3]PR。

The beta-CD [3]]Of PR¹The H NMR spectrum showed a molar ratio of beta-CD to axial polymer of 1.98: 1.

The beta-CD [3]]The gel permeation chromatography of PR did not detect the free β -CD efflux peak and possessed a larger molecular weight than the axial polymer, demonstrating the formation of a mechanical interlock structure for PR. Results¹The result of H NMR spectrum proves that the beta-CD 3]The insertion amount of beta-CD in PR was 2.

The test result shows that the beta-CD 3 PR takes polytetrahydrofuran ether diamine containing ferrocene inclusion site structure in the middle of molecular chain as the axial polymer, beta-CD as the main molecule embedded in the axial polymer, and the two ends of the axial polymer are blocked by triphenyl glycine to form a mechanical interlocking structure; the insertion amount of the beta-CD is 2, and the ferrocene and the polyethylene glycol diamine are connected through an amide bond.

Example 5

A method for preparing beta-CD 3 PR, the method comprises the following steps:

(1) 1 part of PTHF2000, 12.0 parts of CDI and dry THF in an amount of 9 times the mass of PTHF2000 were charged into a reaction vessel, mixed uniformly under nitrogen protection and reacted at 35 ℃ for 24 hours. Adding 60 parts of ethylenediamine, continuously reacting for 24 hours at 35 ℃ under the protection of nitrogen, carrying out rotary evaporation and concentration on the obtained solution, adding dichloromethane which is equal to 18 times of PTHF2000 parts by mass, uniformly mixing, pouring into a liquid separation device, adding saturated salt water which is equal to 0.2 times of dichloromethane in volume, fully oscillating, washing, standing for 5min, separating out an organic phase, and repeatedly washing for 3 times. 20 parts of anhydrous magnesium sulfate are added and sufficiently shaken, the liquid phase is filtered after 5min, retained and evaporated and concentrated, and then precipitated in 50 parts of glacial ethyl ether, and the precipitate is collected and dried under vacuum to obtain 0.85 part of PTHF2000 diamine.

(2) Adding 0.2 part of 1,1 '-ferrocene dicarboxylic acid, 0.5 part of PyBOP, 0.5 part of N, N-diisopropylethylamine and 50 times of mass part of DMF (dimethyl formamide) equivalent to 1, 1' -ferrocene dicarboxylic acid into a reaction container, stirring at normal temperature for 5min, adding 0.85 part of PTHF2000 diamine, stirring at 35 ℃ for 24h, performing rotary evaporation concentration on the obtained solution, adding 2 parts of deionized water, dialyzing in the deionized water for 9h by using a 2000D cellulose dialysis bag, and replacing the dialysate every 3 h. And (3) freeze-drying the dialysate to obtain 0.1 part of axial polymer containing the ferrocene preset inclusion sites.

(3) 0.1 part of the axial polymer and 0.6 part of beta-CD are mixed and stirred in deionized water with the mass part being 60 times that of the beta-CD for 5 days at the temperature of 35 ℃, and the mixture is blown and dried for 24 hours at the temperature of 80 ℃ to obtain the beta-CD-PPR.

(4) In a reaction vessel, 0.1 part of the beta-CD-PPR, 0.9 part of trityl glycine, 0.97 part of BOP, 0.97 part of N, N-diisopropylethylamine, THF and CH in a volume ratio of 1:1 corresponding to 15 mass parts of the beta-CD-PPR were added₃CN mixed solvent, stirred at 35 ℃ for 24 hours, the resulting suspension was subjected to solid-liquid separation, and the solid was washed with 1.5 parts of THF2 times and 1.5 parts of CH₃CN washing for 2 times, washing with 1.5 parts of acetone for 2 times, dissolving in 1 part of DMSO, dialyzing in deionized water for 6 days by using 2000D cellulose dialysis bag, and freeze-drying to obtain 0.019 parts of beta-CD 3]PR。

The beta-CD [3]]Of PR¹H NMR spectrum showed moles of beta-CD to axial polymerThe molar ratio was 1.96: 1.

The beta-CD [3]]The gel permeation chromatography of PR does not detect the free β -CD efflux peak and possesses a larger molecular weight than the axial polymer, demonstrating the formation of PR mechanical interlock structures. Results¹The result of H NMR spectrum proves that the beta-CD 3]The amount of beta-CD insertion in PR was 2.

The calculated molar yield is 19%, the beta-CD 3 PR shows a swelling state similar to gel after being soaked in water for 24 hours, and can be dissolved in DMSO and DMF.

Example 6

A method for preparing beta-CD 3 PR comprises the following steps:

(1) same as example 1, step (1).

(2) Adding 0.2 part of 1, 4-adamantanedicarboxylic acid, 0.45 part of PyBOP, 0.45 part of N, N-diisopropylethylamine and 50 times of mass part of DMF (dimethyl formamide) equivalent to 1, 4-adamantanedicarboxylic acid into a reaction container, stirring at normal temperature for 5min, adding 0.75 part of PEG1000 diamine, stirring at 25 ℃ for 24h, performing rotary evaporation and concentration on the obtained solution, adding 2 parts of deionized water, dialyzing in the deionized water for 9h by using a 1000D cellulose dialysis bag, and replacing the dialysate every 3 h. And (3) freeze-drying the dialysate to obtain 0.1 part of axial polymer containing the ferrocene preset inclusion sites.

(3) 0.1 part of the axial polymer and 0.5 part of beta-CD are mixed and stirred in deionized water with the mass part being 80 times of that of the beta-CD for 5 days at the temperature of 45 ℃, and the mixture is blown and dried for 24 hours at the temperature of 80 ℃ to obtain the beta-CD-PPR.

(4) The beta-CD-PPR, 0.8 part of trityl glycine, 0.85 part of BOP, 0.85 part of N, N-diisopropylethylamine, THF and CH with a volume ratio of 1:1 which is equivalent to 12 times of the mass part of the beta-CD-PPR are added into a reaction container₃CN mixed solvent, stirring at 25 deg.C for 24h, separating solid from liquid, washing solid with 1.5 parts THF for 3 times, washing with 1.5 parts acetone for 2 times, dissolving in 1 part DMSO, dialyzing with 2000D cellulose dialysis bag in deionized water for 6 days, and freeze drying to obtain 0.023 parts beta-CD 3]PR。

The beta-CD [3]]Of PR¹The H NMR spectrum showed a molar ratio of beta-CD to axial polymer of 2.10: 1.

The beta-CD [3]]The gel permeation chromatography of PR did not detect the free β -CD efflux peak and possessed a larger molecular weight than the axial polymer, demonstrating the formation of a mechanical interlock structure for PR. Results¹The result of H NMR spectrum proves that the beta-CD 3]The amount of beta-CD insertion in PR was 2.

The test result shows that the beta-CD 3 PR takes polyethylene glycol diamine containing an adamantane inclusion site structure in the middle of a molecular chain as a shaft polymer, beta-CD as a main molecule embedded in the shaft polymer in a penetrating way, and the two ends of the shaft polymer are blocked by triphenylglycine to form a mechanical interlocking structure; the insertion amount of the beta-CD is 2, and the adamantane is connected with the polyethylene glycol diamine through an amide bond.

The calculated molar yield is 22%, the beta-CD 3 PR shows a swelling state similar to gel after being soaked in water for 24 hours, and can be dissolved in DMSO and DMF.

Example 7

A method for preparing beta-CD 3 PR, the method comprises the following steps:

(1) same as example 1, step (1).

(2) Adding 0.2 part of azobenzene-4, 4-dicarboxylic acid, 0.5 part of PyBOP, 0.5 part of N, N-diisopropylethylamine and DMF (50 times the mass of azobenzene-4, 4-dicarboxylic acid) into a reaction vessel, stirring at normal temperature for 5min, adding 0.68 part of PEG1000 diamine, stirring at 25 ℃ for 24h, carrying out rotary evaporation concentration on the obtained solution, adding 2 parts of deionized water, dialyzing in the deionized water for 9h by using a 1000D cellulose dialysis bag, and replacing the dialysate every 3 h. And (3) freeze-drying the dialysate to obtain 0.1 part of axial polymer containing the ferrocene preset inclusion sites.

(3) 0.1 part of the axial polymer and 0.4 part of beta-CD are mixed and stirred in deionized water with the mass part being 80 times of that of the beta-CD for 5 days at 25 ℃, and the mixture is blown and dried for 24 hours at 80 ℃ to obtain the beta-CD-PPR.

(4) The beta-CD-PPR, 0.8 part of trityl glycine, 0.85 part of BOP, 0.85 part of N, N-diisopropylethylamine, THF and CH with a volume ratio of 1:1 which is equivalent to 12 times of the mass part of the beta-CD-PPR are added into a reaction container₃CN mixed solvent, stirring at 25 deg.C for 24h, separating solid from liquid, washing solid with 1.5 parts THF for 3 times, washing with 1.5 parts acetone for 3 times, dissolving in 1 part DMSO, dialyzing with 2000D cellulose dialysis bag in deionized water for 6 days, and freeze drying to obtain 0.018 parts beta-CD 3]PR。

The beta-CD [3]]Of PR¹The H NMR spectrum showed a molar ratio of beta-CD to axial polymer of 2.07: 1.

The beta-CD [3]]PR infrared absorption spectrum at 3400cm^-1～3100cm^-1Wave number rangeThe presence of a hydroxyl peak was detected within the enclosure, and preliminary indications were made of the presence of β -CD on the axial polymer. In addition, at 1730cm^-1～1670cm^-1The presence of amide bonds was detected in the wavenumber range.

The test result shows that the beta-CD 3 PR takes polyethylene glycol diamine containing azobenzene inclusion site structure in the middle of the molecular chain as the shaft polymer, beta-CD as the main molecule embedded in the shaft polymer and triphenyl glycine at two ends of the shaft polymer to form mechanical interlocking structure; the insertion amount of the beta-CD is 2, and azobenzene is connected with polyethylene glycol diamine through an amide bond.

The calculated molar yield is 18%, the beta-CD 3 PR presents a swelling state similar to gel after being soaked in water for 24 hours, and can be dissolved in DMSO and DMF.

Comparative example 1

A preparation method of a reticular structure polyurethane cross-linked elastomer comprises the following steps:

(1) 4 parts of PEG4000 are dissolved in 20 parts of dry DMSO and 0.53 part of HMDI is added in N₂Stirring for 8h at 60 ℃ under protection, removing bubbles for 30min at 25 ℃ and under the vacuum degree of-0.04 MPa after the reaction is finished, and obtaining a prepolymer solution;

(2) dissolving 0.45 part of beta-CD and 0.05 part of T-12 in 4 parts of dry DMSO (dimethyl sulfoxide), removing bubbles at 25 ℃ and under the vacuum degree of-0.04 MPa for 10min, adding the mixture into the prepolymer solution, stirring at 25 ℃ for 10min, pouring the mixture into a tetrafluoroethylene mold, continuously curing at 50 ℃ for 48h, cooling, and demolding to obtain the polyurethane cross-linked elastomer PEG-PU-CD-0.4 with the reticular structure.

Comparative example 2

In the comparative example, the feeding molar ratio of beta-CD to PEG4000 is 0.3:1, the feeding molar ratio of HMDI to PEG4000 is 2.04:1, the feeding amount of the catalyst is equal to 0.6 percent of the total mass of the beta-CD and the PEG4000, and the rest is the same as the comparative example 1, so that the polyurethane cross-linked elastomer PEG-PU-CD-0.3 with the reticular structure is obtained.

Comparative example 3

In the comparative example, the feeding molar ratio of beta-CD to PEG4000 is 0.5:1, the feeding molar ratio of HMDI to PEG4000 is 2.04:1, the feeding amount of the catalyst is equal to 0.6 percent of the total mass of the beta-CD and the PEG4000, and the rest is the same as the comparative example 1, so that the polyurethane cross-linked elastomer PEG-PU-CD-0.5 with the reticular structure is obtained.

Comparative example 4

In the comparative example, the feeding molar ratio of beta-CD to PEG4000 is 0.6:1, the feeding molar ratio of HMDI to PEG4000 is 2.04:1, the feeding amount of the catalyst is equal to 0.6 percent of the total mass of the beta-CD and the PEG4000, and the rest is the same as the comparative example 1, so that the polyurethane cross-linked elastomer PEG-PU-CD-0.6 with the reticular structure is obtained.

The mechanical property test results of the polyurethane crosslinked elastomers described in comparative examples 1 to 4 are shown in fig. 6 and 10, and the specific data results are shown in table 4. Tensile testing was carried out using ASTM D638 standard method, with a tensile rate of 20 mm/min. The results of the dynamic mechanical testing of comparative example 1 are shown in fig. 12, and the results of the specific data are shown in table 5.

Example 8

(2) dissolving 1.1 parts of beta-CD 3 PR obtained in example 1 and 0.05 part of T-12 in 4 parts of dry DMSO, removing bubbles at 25 ℃ and under the vacuum degree of-0.04 MPa, adding the solution into the prepolymer solution, stirring for 10min at 25 ℃, pouring the solution into a tetrafluoroethylene mold, continuously curing for 48h at 50 ℃, cooling and demolding to obtain the polyurethane cross-linked elastomer PEG-PU-PR-0.4 with the net structure.

Example 9

In this example, the molar ratio of beta-CD 3 PR to PEG4000 is 0.3:1, the molar ratio of HMDI to PEG4000 is 2.04:1, the amount of catalyst is 0.6% of the total weight of beta-CD 3 PR and PEG4000, and the rest is the same as example 8, to obtain a polyurethane cross-linked elastomer PEG-PU-PR-0.3 with a network structure.

Example 10

In this example, the molar ratio of beta-CD 3 PR to PEG4000 is 0.5:1, the molar ratio of HMDI to PEG4000 is 2.04:1, the amount of catalyst is 0.6% of the total weight of beta-CD 3 PR and PEG4000, and the rest is the same as example 8, to obtain a polyurethane cross-linked elastomer PEG-PU-PR-0.5 with a network structure.

Example 11

In this example, the molar ratio of beta-CD 3 PR to PEG4000 is 0.6:1, the molar ratio of HMDI to PEG4000 is 2.04:1, the amount of catalyst is 0.6% of the total weight of beta-CD 3 PR and PEG4000, and the rest is the same as example 8, to obtain a polyurethane cross-linked elastomer PEG-PU-PR-0.6 with a network structure.

The mechanical property test results of the polyurethane crosslinked elastomers in examples 8 to 11 are shown in fig. 7 and 10, and the specific data results are shown in table 4. Tensile testing was carried out using ASTM D638 standard method, with a tensile rate of 20 mm/min. The results of the dynamic mechanical testing of example 8 are shown in fig. 13, and the results of the specific data are shown in table 5.

TABLE 4

Examples	Sample name	ε_m/％	σ_m/MPa	G_F/MJ·m^-3
					Comparative example 1	PEG-PU-CD-0.4	464±34	16.58±2.75	42.09±3.34
Comparative example 2	PEG-PU-CD-0.3	256±23	6.23±1.65	11.67±1.75
					Comparative example 3	PEG-PU-CD-0.5	414±31	15.92±3.89	41.62±2.75
Comparative example 4	PEG-PU-CD-0.6	353±12	19.95±1.02	42.81±2.11
					Example 8	PEG-PU-PR-0.4	1183±105	22.24±4.55	137.32±6.77
Example 9	PEG-PU-PR-0.3	405±39	8.80±2.41	25.07±2.35
					Example 10	PEG-PU-PR-0.5	704±59	21.91±0.84	86.83±5.41
Example 11	PEG-PU-PR-0.6	439±24	17.01±1.67	50.42±3.63

TABLE 5

DMA test shows that in the temperature range of 30-45 deg.c, because PEG as matrix material has strong crystallization and hydrogen bond, comparative example 1 and example 8 have similar modulus and loss angle, and the slip ring structure provided by beta-CD 3 PR has no obvious effect on the performance of the material in low amplitude deformation (the deformation amount is less than or equal to 0.1%). The crystallization and hydrogen bonding of PEG are gradually destroyed along with the temperature rise, the modulus descending amplitude and the loss angle ascending amplitude of the embodiment 8 exceed those of the comparison example 1, and the modulus of the embodiment 8 is obviously lower than that of the comparison example 1 in the temperature range of more than 55 ℃, which shows that the introduction of the slip ring structure in the beta-CD 3 PR effectively leads the beta-CD as a cross-linking point to provide additional elastic entropy for a polymer network in the movement forms of sliding, rotating and vibrating, and the hardness of the material is reduced; in this temperature range, example 8 was observed to have a larger loss angle over most of the range, indicating that microscopic friction from the motion of the β -CD on the shaft polymer increases the loss under the external force, confirming the damping and dissipation effects of the slip ring structure.

DMA tests show that example 9 possesses lower modulus and better loss angle than comparative example 2 over the temperature range above 55 ℃. Example 10 possessed a lower modulus and a higher loss angle than comparative example 3. Example 11 possessed a lower modulus and a higher loss angle than comparative example 4.

Comparative example 5

(1) 3 parts of PC3000 are dissolved in 15 parts of dry DMSO, 0.53 part of HMDI is added, and the mixture is poured into N₂Stirring for 6h at 65 ℃ under protection, removing bubbles for 30min at 25 ℃ and under the vacuum degree of-0.04 MPa after the reaction is finished, and obtaining a prepolymer solution;

(2) dissolving 0.45 part of beta-CD and 0.08 part of T-12 in 4 parts of dry DMSO (dimethylsulfoxide), removing bubbles at 25 ℃ and under the vacuum degree of-0.04 MPa for 15min, adding the mixture into the prepolymer solution, stirring at 25 ℃ for 10min, pouring the mixture into a tetrafluoroethylene mold, continuously curing at 50 ℃ for 48h, cooling, and demolding to obtain the reticular polyurethane crosslinked elastomer PC-PU-CD-0.4.

Comparative example 6

In the comparative example, the feeding molar ratio of beta-CD to PC3000 is 0.3:1, the feeding molar ratio of HMDI to PC3000 is 2.04:1, the feeding amount of the catalyst is 0.8 percent of the total mass of the beta-CD and the PC3000, and the rest is the same as the comparative example 5, so that the polyurethane cross-linked elastomer PC-PU-CD-0.3 with the reticular structure is obtained.

Comparative example 7

In the comparative example, the feeding molar ratio of beta-CD to PC3000 is 0.5:1, the feeding molar ratio of HMDI to PC3000 is 2.04:1, the feeding amount of the catalyst is 0.8 percent of the total mass of the beta-CD and the PC3000, and the rest is the same as the comparative example 5, so that the polyurethane cross-linked elastomer PC-PU-CD-0.5 with a reticular structure is obtained.

Comparative example 8

In the comparative example, the feeding molar ratio of beta-CD to PC3000 is 0.6:1, the feeding molar ratio of HMDI to PC3000 is 2.04:1, the feeding amount of the catalyst is 0.8 percent of the total mass of the beta-CD and the PC3000, and the rest is the same as the comparative example 5, so that the polyurethane cross-linked elastomer PC-PU-CD-0.6 with the reticular structure is obtained.

The mechanical property test results of the polyurethane crosslinked elastomers described in comparative examples 5 to 8 are shown in fig. 8 and 11, and the specific data results are shown in table 6. Tensile testing was carried out using ASTM D638 standard method, with a tensile rate of 20 mm/min. The results of the dynamic mechanical testing of comparative example 5 are shown in fig. 14, and the results of the specific data are shown in table 7.

Example 12

(1) 3 parts of PC3000 are dissolved in 15 parts of dry DMSO, 0.53 part of HMDI is added, and the mixture is poured into N₂Stirring for 6h at 65 ℃ under protection, removing bubbles for 40 min at 25 ℃ and under the vacuum degree of-0.04 MPa after the reaction is finished, and obtaining a prepolymer solution;

(2) dissolving 1.1 parts of beta-CD 3 PR prepared in example 1 and 0.08 part of T-12 in 4 parts of dry DMSO, removing bubbles at 25 ℃ and under the vacuum degree of-0.04 MPa, adding the solution into the prepolymer solution, stirring for 10min at 25 ℃, pouring the solution into a tetrafluoroethylene mold, continuously curing for 48h at 50 ℃, cooling and demolding to obtain the polyurethane cross-linked elastomer PC-PU-PR-0.4 with the net structure.

Example 13

In this example, the molar ratio of beta-CD 3 PR to PC3000 was 0.3:1, the molar ratio of HMDI to PC3000 was 2.04:1, and the amount of catalyst added was 0.8% of the total mass of beta-CD 3 PR and PC3000, and the rest of the same procedure as in example 12 gave a polyurethane crosslinked elastomer PC-PU-PR-0.3 with a network structure.

Example 14

In this example, the molar ratio of beta-CD 3 PR to PC3000 was 0.5:1, the molar ratio of HMDI to PC3000 was 2.04:1, and the amount of catalyst added was 0.8% of the total mass of beta-CD 3 PR and PC3000, and the rest was the same as in example 12, to obtain a network-structured polyurethane crosslinked elastomer PC-PU-PR-0.5.

Example 15

In this example, the molar ratio of beta-CD 3 PR to PC3000 was 0.6:1, the molar ratio of HMDI to PC3000 was 2.04:1, and the amount of catalyst added was 0.8% of the total mass of beta-CD 3 PR and PC3000, and the rest of the same procedure as in example 12 gave a polyurethane crosslinked elastomer PC-PU-PR-0.6 with a network structure.

The mechanical property test results of the polyurethane crosslinked elastomers described in examples 12 to 15 are shown in fig. 9 and 11, and the specific data results are shown in table 6. Tensile testing was carried out using ASTM D638 standard method, with a tensile rate of 20 mm/min. The results of the dynamic mechanical testing of example 12 are shown in fig. 15, and the results of the specific data are shown in table 7.

TABLE 6

TABLE 7

DMA tests show that example 12 possesses a lower modulus and a higher loss angle than comparative example 5 in the temperature range tested, indicating that with PC as the elastomer base material, crystallization and hydrogen bonding are greatly impaired and the influence of the slip ring structure on the material properties is more pronounced.

DMA tests show that example 13 possesses a lower modulus and better loss angle than comparative example 6 over the test temperature range of 30c to 100 c. Example 14 possessed a lower modulus and a higher loss angle than comparative example 7. Example 15 possessed a lower modulus and a higher loss angle than comparative example 8.

According to the results of examples 1-7, the beta-CD 3 PR provided by the invention uses water-soluble polymer diamine containing a guest small molecule inclusion site structure in the middle position of a molecular chain as an axial polymer, beta-CD as a host molecule embedded in the axial polymer in a penetrating way, and the two ends of the axial polymer are blocked by a substance with the molecular volume larger than the cavity size of the beta-CD to form a mechanical interlocking structure; the insertion amount of the beta-CD is 2, the guest small molecule is a substance capable of being encapsulated with the beta-CD, the water-soluble polymer diamine is a linear polymer with both ends modified by amino groups and the molecular cross section smaller than the cavity size of the beta-CD, the guest small molecule is connected with the water-soluble polymer diamine through an amide bond, and the structural model diagram is shown in figure 16.

According to the results of examples 8-15, the polyurethane crosslinked elastomer obtained by curing and crosslinking the beta-CD 3 PR has high maximum breaking stress, elongation at maximum strength and breaking energy; and has lower elastic modulus and higher loss angle within the range of 30-100 ℃.

In summary, the invention includes but is not limited to the above embodiments, and any equivalent replacement or local modification made under the spirit and principle of the invention should be considered as being within the protection scope of the invention.

Claims

1. A beta-cyclodextrin polyrotaxane with accurate intercalation amount, which is characterized in that: the beta-cyclodextrin polyrotaxane takes water-soluble polymer diamine containing an object small molecule inclusion site structure in the middle position of a molecular chain as a shaft polymer, beta-CD as a main body molecule embedded in the shaft polymer in a penetrating way, and two ends of the shaft polymer are blocked by a substance with the molecular volume larger than the size of a beta-CD cavity to form a mechanical interlocking structure; wherein the insertion amount of the beta-CD is 2, the guest micromolecule is an inclusion micromolecule substance of the beta-CD, the water-soluble polymer diamine is a linear polymer with both ends modified by amino and the molecular sectional area smaller than the cavity size of the beta-CD, and the guest micromolecule is connected with the water-soluble polymer diamine through an amide bond.

2. The beta-cyclodextrin polyrotaxane with accurate intercalation amount according to claim 1, wherein: the guest small molecule is ferrocene, adamantane or azobenzene; the water-soluble polymer diamine is polyether diamine or polyester diamine.

3. The beta-cyclodextrin polyrotaxane with accurate intercalation amount according to claim 2, wherein: the water-soluble polymer diamine is polyethylene glycol diamine, polytetrahydrofuran ether diamine, ethylene oxide/propylene oxide copolyether diamine or ethylene oxide/tetrahydrofuran copolyether diamine, polyethylene glycol succinate diamine, polybutylene glycol succinate diamine or polyhexamethylene glycol succinate diamine; the molecular weight of the water-soluble polymer diamine is 500-4000.

4. A method for preparing the beta-cyclodextrin polyrotaxane with accurate intercalation amount according to any one of claims 1 to 3, comprising the steps of: the method comprises the following steps:

(1) adding a guest micromolecule derivative, water-soluble polymer diamine, a catalyst I for amide condensation, an acid-binding agent I for amide condensation and a solvent I into a reaction container, stirring for 24-48 h at 25-35 ℃ to obtain a solution, concentrating the solution, and dialyzing in water with the purity higher than that of deionized water for 8-10 h to obtain a shaft polymer solution which contains a preset inclusion site and has amino groups at the end groups on two sides; wherein the guest micromolecule derivative is a substance which is included with the beta-CD and contains carboxyl at two ends of the guest micromolecule;

(2) adding the shaft polymer solution and beta-CD into water with the purity higher than that of deionized water at the temperature of 25-45 ℃, mixing and stirring for 4-5 days, and drying to obtain beta-CD-PPR;

(3) adding the beta-CD-PPR, a blocking agent, a catalyst II for amide condensation, an acid-binding agent II for amide condensation and a solvent II into a reaction container, stirring at 25-35 ℃ for 24-48 h to obtain a suspension, carrying out solid-liquid separation on the suspension, washing solids, dissolving the solids into dimethyl sulfoxide, dialyzing in water with the purity higher than that of deionized water for 4-6 days, and drying to obtain the cyclodextrin polyrotaxane with accurate intercalation amount; wherein the solvent II can not dissolve beta-CD-PPR but can dissolve a blocking agent, a catalyst II for amide condensation and an acid-binding agent II for amide condensation.

5. The method for preparing beta-cyclodextrin polyrotaxane with accurate intercalation amount according to claim 4, wherein: in the step (1): the guest small molecule derivative is ferrocene dicarboxylic acid, adamantane dicarboxylic acid or azobenzene dicarboxylic acid; the water-soluble polymer diamine is polyether diamine or polyester diamine; the catalyst I for amide condensation is benzotriazole-1-yl-oxy-tripyrrolidinyl phosphorus hexafluorophosphate; the acid-binding agent I for amide condensation is N, N-diisopropylethylamine or triethylamine; the solvent I is N, N-dimethylformamide; a dialysis bag with the molecular weight cut-off of 0.8-1.2 times of that of the water-soluble polymer diamine is adopted during dialysis;

in the step (3): the end capping agent is more than one of carboxyl triphenylmethane, carboxyl tetraphenyl methane and trityl glycine; the catalyst II for amide condensation is benzotriazole-1-oxyl tris (dimethylamino) phosphonium hexafluorophosphate; the acid-binding agent II for amide condensation is N, N-diisopropylethylamine; the solvent II is a mixed solvent of tetrahydrofuran and acetonitrile with the same volume; and a dialysis bag with the molecular weight cut-off of 1.5-2.5 times of that of the water-soluble polymer diamine is adopted during dialysis.

6. The method for preparing beta-cyclodextrin polyrotaxane with accurate intercalation amount according to claim 4, wherein: in the step (1): the molar ratio of the guest small molecule derivative to the water-soluble polymer diamine to the catalyst I for amide condensation to the acid-binding agent I for amide condensation is 1: 3.3-4.4: 2.1-2.8, and the molar ratio of the catalyst I for amide condensation to the acid-binding agent I for amide condensation is 1: 1; the mass ratio of the solvent I to the guest small molecule derivative is 50: 1-80: 1;

in the step (2): the molar ratio of the shaft polymer to the beta-CD in the shaft polymer solution is more than or equal to 1:2, and the mass ratio of water to the beta-CD is 50: 1-100: 1;

in the step (3): the molar ratio of the beta-CD-PPR, the end-capping agent, the catalyst II for amide condensation and the acid-binding agent II for amide condensation is 1: 8-10: 8.2-10.5, and the molar ratio of the catalyst II for amide condensation and the acid-binding agent II for amide condensation is 1: 1; the mass ratio of the beta-CD-PPR to the solvent II is 15: 1-20: 1.

7. The method for preparing beta-cyclodextrin polyrotaxane with accurate intercalation amount according to claim 4, wherein: in the step (1): the guest small molecule derivative is ferrocene dicarboxylic acid, adamantane dicarboxylic acid or azobenzene dicarboxylic acid; the water-soluble polymer is polyethylene glycol diamine, polytetrahydrofuran ether diamine, ethylene oxide/propylene oxide copolyether diamine, ethylene oxide/tetrahydrofuran copolyether diamine, polyethylene glycol succinate diamine, polybutylene glycol succinate diamine or polyhexamethylene glycol succinate diamine; the molecular weight of the water-soluble polymer diamine is 500-4000; the catalyst I for amide condensation is benzotriazole-1-yl-oxy tripyrrolidinyl phosphorus hexafluorophosphate; the acid-binding agent I for amide condensation is N, N-diisopropylethylamine or triethylamine; the solvent I is N, N-dimethylformamide;

the molar ratio of the guest small molecule derivative to the water-soluble polymer diamine to the catalyst I for amide condensation to the acid-binding agent I for amide condensation is 1: 3.3-4.4: 2.1-2.8, and the molar ratio of the catalyst I for amide condensation to the acid-binding agent I for amide condensation is 1: 1; the mass ratio of the solvent I to the guest small molecules is 50: 1-80: 1;

a dialysis bag with the molecular weight cut-off of 0.8-1.2 times of that of the water-soluble polymer diamine is adopted during dialysis;

in the step (2): the molar ratio of the axial polymer to the beta-CD is 1: 2-1: 20; the mass ratio of the water to the beta-CD is 50: 1-100: 1;

in the step (3): the end capping agent is more than one of carboxyl triphenylmethane, carboxyl tetraphenyl methane and trityl glycine; the catalyst II for amide condensation is benzotriazole-1-oxyl tris (dimethylamino) phosphonium hexafluorophosphate; the acid-binding agent II for amide condensation is N, N-diisopropylethylamine; the solvent II is a mixed solvent of tetrahydrofuran and acetonitrile with the same volume;

the molar ratio of the beta-CD-PPR, the end-capping agent, the catalyst II for amide condensation and the acid-binding agent II for amide condensation is 1: 8-10: 8.2-10.5, and the molar ratio of the catalyst II for amide condensation and the acid-binding agent II for amide condensation is 1: 1; the mass ratio of the beta-CD-PPR to the solvent II is 15: 1-20: 1;

washing with one or more of tetrahydrofuran, acetonitrile, acetone and methanol;

and a dialysis bag with the molecular weight cut-off of 1.5-2.5 times of that of the water-soluble polymer diamine is adopted during dialysis.

8. The use of the beta-cyclodextrin polyrotaxane with accurate intercalation amount according to any one of claims 1 to 3, wherein: the beta-cyclodextrin polyrotaxane is used as a cross-linking agent in the preparation of the damping toughening polymer material.

9. The use of a β -cyclodextrin polyrotaxane with accurate intercalation according to claim 8, wherein: the beta-cyclodextrin polyrotaxane is used as a cross-linking agent in the preparation of the reticular structure polyurethane cross-linked elastomer, and the preparation method comprises the following steps:

(2) dissolving beta-cyclodextrin polyrotaxane and a curing catalyst in a dry solvent IV, removing bubbles at 25-35 ℃ and under the vacuum degree of less than or equal to-0.04 MPa, adding the mixture into the prepolymer solution after 10-30 min of bubble removal, stirring at 25-35 ℃ for 10-15 min, pouring the mixture into a mold, continuously curing for more than 48h at 50-60 ℃, cooling and demolding to obtain the polyurethane crosslinked elastomer with the reticular structure.

10. The use of a β -cyclodextrin polyrotaxane with accurate intercalation according to claim 9, wherein: the polymer diol is more than one of polyether diol, polyester diol and polycarbonate diol;

the diisocyanate is more than one of 4,4 '-dicyclohexylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, L-lysine ethyl ester diisocyanate, tetramethylene diisocyanate, diphenylmethane-4, 4' -diisocyanate and 2, 4-toluene diisocyanate;

the curing catalyst is more than one of organic tin catalyst and organic base catalyst;

the solvent III and the solvent IV are respectively and independently more than one of dimethyl sulfoxide, N-dimethylformamide, dimethylacetamide and N-methylpyrrolidone;

the diisocyanate is 2.05 to 2.15 times of the molar weight of the polymer diol, and the molar ratio of the cyclodextrin polyrotaxane to the polymer diol is more than or equal to 0.3: 1; the mass of the curing catalyst is 0.5-0.8% of the total mass of the cyclodextrin polyrotaxane and the polymer diol.

11. The use of a β -cyclodextrin polyrotaxane with accurate intercalation according to claim 10, wherein: the polymer diol is more than one of polyethylene glycol, polypropylene glycol, polytetrahydrofuran, ethylene oxide/propylene oxide copolyether, ethylene oxide/tetrahydrofuran copolyether diol, polyethylene glycol succinate, polybutylene succinate, polyethylene glycol succinate diol, poly (1, 4-butanediol carbonate diol) and poly (1, 6-hexanediol carbonate diol); the polymer diol has a functionality of 1.85 to 2.15 and a number average molecular weight of 2000 to 10000.

12. The use of a β -cyclodextrin polyrotaxane with accurate intercalation according to claim 10, wherein: the curing catalyst is more than one of dibutyltin dilaurate, stannous octoate, triethylamine, 1, 4-diazabicyclo [2.2.2] octane, dimethylamino ethyl ether and 1, 8-diazabicyclo [5.4.0] undec-7-ene.

13. The use of a β -cyclodextrin polyrotaxane with accurate intercalation according to claim 10, wherein: the molar ratio of the cyclodextrin polyrotaxane to the polymer glycol is 0.3: 1-0.6: 1.