Epoxy resin polyrotaxane network lubricating material, and preparation method and application thereof

Abstract

The application discloses an epoxy resin polyrotaxane network lubricating material, a preparation method thereof and application of the epoxy resin polyrotaxane network lubricating material in preparation of biological lubricating materials. The epoxy resin polyrotaxane network lubricating material is obtained through ring-opening and curing reaction of a polyethylene glycol and cyclodextrin quasi-polyrotaxane, an epoxy resin monomer and a curing agent polyether amine. In the polyethylene glycol and cyclodextrin quasi-polyrotaxane, the molar ratio of the polyethylene glycol and the cyclodextrin is 1-100:1-2000; the molar ratio of the epoxy resin monomer, the curing agent polyether amine and the polyethylene glycol and cyclodextrin quasi-polyrotaxane is 100-2000:50-1000:0.1-200. The preparation method comprises the following steps: performing ring-opening and curing reaction of the polyethylene glycol and cyclodextrin quasi-polyrotaxane, the epoxy resin monomer and the curing agent polyether amine to obtain the epoxy resin polyrotaxane network lubricating material.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of tribology, in particular to an epoxy resin polyrotaxane network lubricating material and a preparation method and application thereof. BACKGROUND

[0002] Mechanically interlocked molecules have unique topological structure and intramolecularly confined motion space, and the connection of mechanical bonds makes the molecules have overall structural stability and dynamics, so they are often used to construct functional polymer materials.

[0003] As the product of the cross-fusion of mechanically interlocked structure and polymer materials, the rotaxane-type polymer has a special free sliding and rotating phenomenon, which can convert the sliding friction of the friction interface into rolling friction, effectively reducing the friction coefficient. In addition, the large steric hindrance of the rotaxane structure can form a buffer zone on the friction interface, effectively reducing the wear between the friction pairs.

[0004] Therefore, the rotaxane polymer is a novel and very potential bulk friction material, and is also an ideal choice for improving the wear resistance, toughness and biocompatibility of the coating of biomedical implant devices.

[0005] In addition, the rotaxane polymer has low raw material cost, simple preparation process, cavity structure, pulley effect and good viscoelasticity, and is an important research direction of new bulk lubricating materials.

[0006] The rotaxane structure will keep rotating and sliding along the surface of the friction pair under the action of friction, which not only reduces the friction force of the friction interface, but also prevents the direct contact of the friction pair surface, thereby reducing the wear.

[0007] At present, cyclodextrin is one of the most widely used host molecules in supramolecular chemistry, which has low raw material cost, non-toxicity, good biocompatibility and simple preparation process, and has high scientific research value as an application material.

[0008] The present application mainly selects polyrotaxane with cyclodextrin as host-guest molecules as the research object, and constructs an epoxy resin polyrotaxane lubricating network, which has very important research significance for the development of new rotaxane lubricating materials.

[0009] To date, there have been few reports on the application of mechanically interlocking polymers in biomedical materials and devices. Therefore, this invention selects cyclodextrin, a macrocycle with excellent biocompatibility, and utilizes host-guest recognition to form a quasi-polyrotaxane with polyethylene glycol. This quasi-polyrotaxane is then reacted with epoxy resin and a curing agent to obtain an epoxy resin polyrotaxane lubricating network. This polymer network exhibits excellent tribological properties and can serve as a novel supramolecular material for biomedical applications. Such new materials can make a positive contribution to extending the lifespan of biomedical implantable devices in the human body. Simultaneously, this opens up an important research direction at the intersection of supramolecular, polymer, and biomedical device fields, and will also provide possibilities for the application of functional supramolecular and polymeric materials in the medical and medical device fields. Summary of the Invention

[0010] This invention provides an epoxy resin polyrotaxane network lubricating material, its preparation method, and its applications. The method of this invention is simple, with mild reaction conditions, and is easy to implement. Compared with traditional lubricating materials, the lubricating network of this invention exhibits dynamic properties, good biocompatibility, and excellent mechanical properties, showing potential for application in bio-lubricating coatings and high-end lubrication fields.

[0011] [1] An epoxy resin polyrotaxane network lubricant (MIB), wherein the epoxy resin polyrotaxane network lubricant is obtained by ring-opening and curing reaction of polyethylene glycol and cyclodextrin quasi-polyrotaxane (PR) with epoxy resin monomers and curing agent polyetheramine;

[0012] In the quasi-polyrotaxane of polyethylene glycol and cyclodextrin, the molar ratio of polyethylene glycol to cyclodextrin is 1-100:1-2000, preferably 1:2-10, and more preferably 1:5;

[0013] The molar ratio of epoxy resin monomers, curing agent polyetheramine, and quasi-polyrotaxane of polyethylene glycol and cyclodextrin is 100-2000:50-1000:0.1-200.

[0014] The number-average molecular weight of the quasi-polyrotaxane of polyethylene glycol and cyclodextrin can be 1,000 to 500,000 g / mol.

[0015] In the quasi-polyrotaxane of polyethylene glycol and cyclodextrin, the number average molecular weight of polyethylene glycol is 600-5000 g / mol, preferably 600-2000 g / mol, and more preferably 2000 g / mol.

[0016] The epoxy resin monomer may be at least one of bisphenol A diglycidyl ether (DGEBA), polyethylene glycol diglycidyl ether, and trimethylolpropane triglycidyl ether.

[0017] The curing agent, polyetheramine, may be at least one of polyetheramine D230, polyetheramine D400 (PEA400), and polyetheramine D2000.

[0018] In some embodiments, the curing reaction conditions are: temperature 0–180°C (e.g., 80–100°C, etc.) and time 2–72 hours.

[0019] In some embodiments, the ring-opening and curing reaction temperature is 60–100°C.

[0020] The cyclodextrin may be at least one of α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin.

[0021] The end-capping groups of the polyethylene glycol may be one or more of hydroxyl, amino, mercapto, and carboxyl groups.

[0022] The quasi-polyrotaxane of polyethylene glycol and cyclodextrin can be formed by host-guest recognition of polyethylene glycol and cyclodextrin in water. An example method for preparing the quasi-polyrotaxane of polyethylene glycol and cyclodextrin is as follows:

[0023] At room temperature, add an aqueous solution of polyethylene glycol dropwise to the aqueous solution of cyclodextrin, stir thoroughly, and then let stand to allow the cyclodextrin to completely coat the polyethylene glycol molecular chain.

[0024] After cyclodextrin and polyethylene glycol undergo host-guest recognition, a water-insoluble quasi-polyrotaxane is produced. A large amount of white precipitate is obtained by precipitation and centrifugation. The white precipitate is washed repeatedly with deionized water to ensure that unreacted cyclodextrin and polyethylene glycol are washed away.

[0025] Finally, freeze-drying yielded a white solid powder, namely a quasi-polyrotaxane of polyethylene glycol and cyclodextrin.

[0026] This invention yields quasi-polyrotaxanes from polyethylene glycol and cyclodextrin in an aqueous phase, followed by a ring-opening reaction with epoxy resin monomers and a curing agent, polyetheramine, to obtain an epoxy resin polyrotaxane lubricating network. Compared with traditional polymer friction materials, the lubricating network of this invention exhibits dynamic properties, good biocompatibility, and excellent mechanical properties. Importantly, the lubrication mechanism of this type of lubricating material is mainly based on rolling friction, resulting in better friction reduction performance than traditional sliding friction materials. Therefore, it has application potential in bio-lubricating coatings and high-end lubrication fields.

[0027] [2] According to the preparation method of epoxy resin polyrotaxane network lubricating material described in [1], the epoxy resin polyrotaxane network lubricating material is obtained by ring-opening and curing reaction of polyethylene glycol and cyclodextrin quasi-polyrotaxane with epoxy resin monomers and curing agent polyetheramine.

[0028] [3] Application of epoxy resin polyrotaxane network lubricating material according to [1] in the preparation of bio-lubricating materials.

[0029] The epoxy resin polyrotaxane network lubricant of the present invention exhibits excellent lubricity under friction conditions of 0.1 to 50 N.

[0030] In the epoxy resin polyrotaxane network lubricant of the present invention, the addition amount of polyethylene glycol and cyclodextrin quasi-polyrotaxane is 0.01wt% to 20wt% (e.g., 0.5wt% to 3wt%, further 2wt% to 2.5wt%, etc.) (based on the total mass of polyethylene glycol and cyclodextrin quasi-polyrotaxane, epoxy resin monomers and curing agent polyetheramine being 100%), exhibiting excellent lubricity.

[0031] Compared with the prior art, the beneficial effects of this invention are as follows:

[0032] 1) This invention provides an epoxy resin polyrotaxane lubricating network with excellent performance, easy synthesis, and mild synthesis conditions. The epoxy resin polyrotaxane lubricating network has dynamic properties, good biocompatibility, and excellent mechanical properties. Importantly, the lubrication mechanism of this type of lubricating material is mainly based on rolling friction, which has better friction reduction performance than traditional sliding friction materials. Therefore, it has application potential in bio-lubricating coatings and high-end lubrication fields.

[0033] 2) The epoxy resin polyrotaxane lubricating network provided by this invention reduces the coefficient of friction by about 20% and improves the anti-wear performance by about 2 times under conditions where the amount of quasi-polyrotaxane added to cyclodextrin polyethylene glycol is 0.5wt% to 2.5wt%. Cytotoxicity experiments showed that this lubricating network has good biocompatibility. Attached Figure Description

[0034] Figure 1 This is a schematic diagram illustrating the preparation of an epoxy resin polyrotaxane network lubricating material.

[0035] Figure 2 Differential scanning calorimetry (DSC) curves of the polymer networks prepared in Example 2 and Comparative Example 2 are shown.

[0036] Figure 3 The stress-strain curves are for the polymer networks obtained in Example 2 and Comparative Example 2.

[0037] Figure 4 The graph shows the mechanical properties of the polymer networks obtained in Example 2 and Comparative Example 2.

[0038] Figure 5 The dynamic friction coefficient curves are for medical titanium alloy (Ti) and polymer networks prepared in Examples 1-3 and Comparative Examples 1-3.

[0039] Figure 6 The bar chart shows the average friction coefficient of the medical titanium alloy (Ti) and the polymer networks prepared in Examples 1-3 and Comparative Examples 1-3, under test conditions of 2N load and 1Hz frequency.

[0040] Figure 7 The diagram shows the lubrication performance of medical titanium alloy (Ti) and polymer networks prepared in Examples 1-3 and Comparative Examples 1-3 under a load of 10N and a frequency of 2Hz.

[0041] Figure 8 The diagram shows the lubrication performance of medical titanium alloy (Ti) and polymer networks prepared in Examples 1-3 and Comparative Examples 1-3 under a load of 1N and a frequency of 2Hz.

[0042] Figure 9 The diagram shows the lubrication performance of medical titanium alloy (Ti) and polymer networks prepared in Examples 1-3 and Comparative Examples 1-3 under a 5N load and a 2Hz frequency.

[0043] Figure 10 The diagram shows the lubrication performance of medical titanium alloy (Ti) and polymer networks prepared in Examples 1-3 and Comparative Examples 1-3 under a 5N load and a 5Hz frequency.

[0044] Figure 11 The wear rate histograms are for medical titanium alloy (Ti) and polymer networks prepared in Examples 1-3 and Comparative Examples 1-3.

[0045] Figure 12 The diagram shows the lubrication performance of medical titanium alloy (Ti) and epoxy resin polyrotaxane lubrication networks with different contents of PR2000 under 2N load and 1Hz frequency conditions.

[0046] Figure 13 Cytotoxicity diagrams of medical titanium alloy (Ti), epoxy resin without polyrotaxane (NOPR), and polymer networks prepared in Example 2 and Comparative Example 2.

[0047] Figure 14 The graph shows the cytotoxicity of the polymer networks obtained in Examples 1 and 3 and Comparative Examples 1 and 3. Detailed Implementation

[0048] The present invention will be further described below with reference to the accompanying drawings and specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention.

[0049] Example 1

[0050] A schematic diagram of the preparation of epoxy resin polyrotaxane network lubricating material is shown below. Figure 1 As shown.

[0051] Bisphenol A diglycidyl ether (3.4 g, 10.0 mmol), cyclodextrin polyethylene glycol quasi-polyrotaxane (0.135 g, PR600), and polyetheramine D400 (2.0 g, 5 mmol) were mixed in a 50 mL plastic bottle. The cyclodextrin in the cyclodextrin polyethylene glycol quasi-polyrotaxane PR600 was α-cyclodextrin, the end-capping group of the polyethylene glycol was carboxyl, the number-average molecular weight of the polyethylene glycol was 600 g / mol, and the molar ratio of polyethylene glycol to cyclodextrin was 1:2. The mixture was homogenized using a homogenizer. The epoxy resin prepolymer was transferred to a polytetrafluoroethylene mold and reacted in an oven at 80–100 °C for 6 hours to obtain a transparent epoxy resin polyrotaxane lubricating network MIB-1.

[0052] Example 2

[0053] A schematic diagram of the fabrication of the epoxy resin polyrotaxane lubrication network is shown below. Figure 1 As shown.

[0054] Bisphenol A diglycidyl ether (3.4 g, 10.0 mmol), cyclodextrin polyethylene glycol quasi-polyrotaxane (0.135 g, PR2000), and polyetheramine D400 (2.0 g, 5 mmol) were mixed in a 50 mL plastic bottle. The cyclodextrin in the cyclodextrin polyethylene glycol quasi-polyrotaxane PR2000 was α-cyclodextrin, the end-capping group of the polyethylene glycol was carboxyl, the number-average molecular weight of the polyethylene glycol was 2000 g / mol, and the molar ratio of polyethylene glycol to cyclodextrin was 1:5. The mixture was homogenized using a homogenizer. The epoxy resin prepolymer was transferred to a polytetrafluoroethylene mold and reacted in an oven at 80–100 °C for 6 hours to obtain a transparent epoxy resin polyrotaxane lubricating network MIB-2 (or denoted as MIB-2-2.0%).

[0055] Following the above process, by changing the amount of quasi-polyrotaxane PR2000 of cyclodextrin polyethylene glycol to 0.0335g, 0.0675g, and 0.101g, respectively, epoxy resin polyrotaxane lubricating networks MIB-2-0.5%, MIB-2-1.0%, and MIB-2-1.5% were obtained.

[0056] Example 3

[0057] A schematic diagram of the fabrication of the epoxy resin polyrotaxane lubrication network is shown below. Figure 1 As shown.

[0058] Bisphenol A diglycidyl ether (3.4 g, 10.0 mmol), cyclodextrin polyethylene glycol quasi-polyrotaxane (0.135 g, PR5000), and polyetheramine D400 (2.0 g, 5 mmol) were mixed in a 50 mL plastic bottle. The cyclodextrin in the cyclodextrin polyethylene glycol quasi-polyrotaxane PR5000 was α-cyclodextrin, the end-capping group of the polyethylene glycol was carboxyl, the number-average molecular weight of the polyethylene glycol was 5000 g / mol, and the molar ratio of polyethylene glycol to cyclodextrin was 1:10. The mixture was homogenized using a homogenizer. The epoxy resin prepolymer was transferred to a polytetrafluoroethylene mold and reacted in an oven at 80–100 °C for 6 hours to obtain a transparent epoxy resin polyrotaxane lubricating network MIB-3.

[0059] Comparative Example 1

[0060] The only difference between the preparation method of the polymer network in this comparative example and that in Example 1 is that the quasi-polyrotaxane of cyclodextrin polyethylene glycol is replaced with an equal mass of carboxyl-terminated polyethylene glycol PEG (number average molecular weight Mn = 600 g / mol) to prepare a rotaxane-free polymer network Control-1.

[0061] Comparative Example 2

[0062] The only difference between the preparation method of the polymer network in this comparative example and that in Example 2 is that the quasi-polyrotaxane of cyclodextrin polyethylene glycol is replaced with an equal mass of carboxyl-terminated polyethylene glycol PEG (number average molecular weight Mn = 2000 g / mol) to prepare a rotaxane-free polymer network Control-2.

[0063] Comparative Example 3

[0064] The only difference between the preparation method of the polymer network in this comparative example and that in Example 3 is that the quasi-polyrotaxane of cyclodextrin polyethylene glycol is replaced with an equal mass of carboxyl-terminated polyethylene glycol PEG (number average molecular weight Mn = 5000 g / mol), and a rotaxane-free polymer network Control-3 is prepared.

[0065] Sample Analysis

[0066] The performance of the polymer networks prepared in Example 2 and Comparative Example 2 was tested. Figure 2 The figure shows the differential scanning calorimetry (DSC) curves of the polymer networks obtained in Example 2 and Comparative Example 2. The figure shows the glass transition temperature (Tg) of the quasi-polyrotaxane polymer network after the addition of cyclodextrin polyethylene glycol. g The slight increase indicates that the aggregation effect and hydrogen bonding of cyclodextrin increase the crosslinking density of the polymer network. Figure 3 The stress-strain curves of the polymer networks prepared in Example 2 and Comparative Example 2 show that the rigidity of the entire polymer is greater after the addition of cyclodextrin polyethylene glycol quasi-polyrotaxane.Figure 4 The bar chart shows the mechanical properties of the polymer networks obtained in Example 2 and Comparative Example 2. As can be seen from the figure, the maximum tensile strength and Young's modulus of the polymer network increased after the addition of cyclodextrin polyethylene glycol quasi-polyrotaxane, which also indicates that the rigidity of the entire polymer network increased.

[0067] Figure 5 and Figure 6 The graphs show the friction reduction properties of the polymer networks obtained in Examples 1-3 and Comparative Examples 1-3. As can be seen from the graphs, the coefficient of friction (COF) of the polymer network decreased after the addition of cyclodextrin polyethylene glycol quasi-polyrotaxane, indicating that the polyrotaxane produced a rolling friction effect under frictional conditions, giving it good friction reduction properties. Figures 7-10 The graphs show the lubrication performance of Examples 1-3 and Comparative Examples 1-3 under different friction conditions (load and frequency). It can be seen that the lubrication performance of the examples improves with increasing load and frequency, indicating that under these conditions, the rolling effect of cyclodextrin is advantageous, resulting in a lower coefficient of friction for the examples. Figure 11 The diagram shows the wear resistance of the polymer networks obtained in Examples 1-3 and Comparative Examples 1-3. It can be seen that the wear rate of the polymer network decreased after the addition of cyclodextrin polyethylene glycol quasi-polyrotaxane. Figure 12 The diagram shows the lubrication performance of the epoxy resin polyrotaxane lubrication network under different concentrations of PR2000. It can be seen that the epoxy resin polyrotaxane lubrication network exhibits good lubricity even at low concentrations of PR2000. Figure 13 and Figure 14 The figures show the cytotoxicity of the polymer networks obtained in Examples 1-3. It can be seen that there was no obvious cell death in the polymer networks after the addition of cyclodextrin polyethylene glycol quasi-polyrotaxane, indicating that the polymer lubricating material has good biocompatibility.

[0068] Furthermore, it should be understood that after reading the above description of the present invention, those skilled in the art can make various alterations or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims.

Claims

1. The application of an epoxy resin polyrotaxane network lubricant in the preparation of bio-lubricating materials, characterized in that, The epoxy resin polyrotaxane network lubricant is obtained by ring-opening and curing reaction of quasi-polyrotaxane of polyethylene glycol and cyclodextrin with epoxy resin monomers and curing agent polyetheramine. In the quasi-polyrotaxane of polyethylene glycol and cyclodextrin, the molar ratio of polyethylene glycol to cyclodextrin is 1:5; The molar ratio of epoxy resin monomers, curing agent polyetheramine, and quasi-polyrotaxane of polyethylene glycol and cyclodextrin is 100-2000:50-1000:0.1-200; In the quasi-polyrotaxane of polyethylene glycol and cyclodextrin, the number-average molecular weight of polyethylene glycol is 2000 g / mol.

2. The application according to claim 1, characterized in that, The number-average molecular weight of the quasi-polyrotaxane of polyethylene glycol and cyclodextrin is 1,000 to 500,000 g / mol.

3. The application according to claim 1, characterized in that, The epoxy resin monomer is at least one of bisphenol A diglycidyl ether, polyethylene glycol diglycidyl ether, and trimethylolpropane triglycidyl ether.

4. The application according to claim 1, characterized in that, The curing agent, polyetheramine, is at least one of polyetheramine D230, polyetheramine D400, and polyetheramine D2000.

5. The application according to claim 1, characterized in that, Curing reaction conditions: temperature 0~180℃, time 2~72 hours.

6. The application according to claim 1, characterized in that, The cyclodextrin is at least one of α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin.

7. The application according to claim 1, characterized in that, The end-capping groups of the polyethylene glycol are one or more of hydroxyl, amino, mercapto, and carboxyl groups.

8. The application according to claim 1, characterized in that, The quasi-polyrotaxane of polyethylene glycol and cyclodextrin is formed by the host-guest recognition of polyethylene glycol and cyclodextrin in water.

9. The application according to any one of claims 1 to 8, characterized in that, The preparation method of the epoxy resin polyrotaxane network lubricating material is as follows: the quasi-polyrotaxane of polyethylene glycol and cyclodextrin is subjected to ring-opening and curing reaction with epoxy resin monomers and curing agent polyetheramine to obtain the epoxy resin polyrotaxane network lubricating material.

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