Epoxy resin polyrotaxane network lubricating material as well as preparation method and application thereof

Abstract

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

Description

Technical Field

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

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

[0003] Rotaxane polymers are the product of the cross-fusion of mechanical interlocking structures and polymer materials. The rotaxane structure is similar to a "wheel" and has a special free sliding and rotation phenomenon. It can transform the sliding friction of the friction interface into rolling friction, effectively reducing its friction coefficient. In addition, due to the large steric hindrance of the rotaxane structure, a buffer zone can be formed on the friction interface, effectively reducing the wear between the friction pairs.

[0004] Therefore, rotaxane polymers are a class of novel and highly promising bulk friction materials, and are also an ideal choice for improving the wear resistance, toughness, and biocompatibility of coatings on biomedical implants.

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

[0006] Under the action of friction, the rotaxane structure will continuously rotate and slide along the friction pair surface, which not only reduces the friction force of the friction interface, but also prevents direct contact between the friction pair surfaces, thereby reducing wear.

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

[0008] The present invention mainly selects polyrotaxane with cyclodextrin as the main guest molecule 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] So far, there are few reports on the application of mechanical interlocking polymers in biomedical materials and devices. Based on this, the present invention selects cyclodextrin with excellent biocompatibility as a macrocycle, utilizes host-guest recognition to form a pseudopolyrotaxane with polyethylene glycol, and then reacts with epoxy resin and a curing agent to obtain an epoxy resin polyrotaxane lubricating network. The polymer network has excellent tribological properties and can be used as a new biomedical supramolecular material. This type of new material makes a positive contribution to extending the service life of biomedical implants in the human body. At the same time, this opens up an important research direction for the intersection of supramolecular, polymer and biomedical devices, and will also make it possible to apply functional supramolecular and polymer materials in the fields of medicine and medical devices. Summary of the invention

[0010] The present invention provides an epoxy resin polyrotaxane network lubricating material and a preparation method and application thereof. The method of the present invention is simple, the reaction conditions are mild, and it is easy to implement; compared with traditional lubricating materials, the lubricating network of the present invention has dynamics and good biocompatibility, and has excellent mechanical properties, and has application potential in the field of biological lubricating coatings and high-end lubrication.

[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 a pseudopolyrotaxane (PR) of polyethylene glycol and cyclodextrin with an epoxy resin monomer and a curing agent polyetheramine;

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

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

[0014] The number average molecular weight of the pseudopolyrotaxane of polyethylene glycol and cyclodextrin may be 1000 to 500000 g / mol.

[0015] In the pseudopolyrotaxane of polyethylene glycol and cyclodextrin, the number average molecular weight of polyethylene glycol is 600 to 5000 g / mol, preferably 600 to 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 to 180° C. (eg, 80 to 100° C., etc.), and time 2 to 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, thiol and carboxyl groups.

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

[0023] At room temperature, add the aqueous solution of polyethylene glycol dropwise to the aqueous solution of cyclodextrin, stir thoroughly, and then let stand to allow the cyclodextrin to be completely wrapped around the polyethylene glycol molecular chain;

[0024] After the host-guest recognition between cyclodextrin and polyethylene glycol occurs, water-insoluble pseudopolyrotaxane is produced, and a large amount of white precipitate is obtained by precipitation and centrifugation. The white precipitate is washed with deionized water for many times to ensure that the unreacted cyclodextrin and polyethylene glycol are washed away.

[0025] Finally, freeze-drying was performed to obtain a white solid powder, which is a pseudopolyrotaxane of polyethylene glycol and cyclodextrin.

[0026] The present invention obtains a pseudopolyrotaxane from polyethylene glycol and cyclodextrin in an aqueous phase, and then carries out a ring-opening reaction with an epoxy resin monomer and a curing agent polyetheramine to obtain an epoxy resin polyrotaxane lubrication network. Compared with traditional polymer friction materials, the lubrication network of the present invention has dynamics and good biocompatibility, as well as excellent mechanical properties. Importantly, the lubrication mechanism of this type of lubricating material is mainly based on rolling friction, and it has better friction reduction performance than traditional sliding friction materials. Therefore, it has application potential in the fields of biological lubricating coatings and high-end lubrication.

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

[0028] [3] Use of the epoxy resin polyrotaxane network lubricating material according to [1] in the preparation of a biological lubricating material.

[0029] The epoxy resin polyrotaxane network lubricating material of the present invention has excellent lubricity under the friction condition of 0.1-50N.

[0030] In the epoxy resin polyrotaxane network lubricating material of the present invention, the added amount of the pseudo-polyrotaxane of polyethylene glycol and cyclodextrin has excellent lubricity at a concentration of 0.01wt% to 20wt% (for example, 0.5wt% to 3wt%, further 2wt% to 2.5wt%, etc.) (based on the total mass of the pseudo-polyrotaxane of polyethylene glycol and cyclodextrin, epoxy resin monomers and curing agent polyetheramine as 100%).

[0031] Compared with the prior art, the present invention has the following beneficial effects:

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

[0033] 2) The epoxy resin polyrotaxane lubricating network provided by the present invention has a friction coefficient reduced by about 20% and an anti-wear performance improved by about 2 times when the addition amount of cyclodextrin polyethylene glycol pseudo-polyrotaxane is 0.5wt% to 2.5wt%. Through cytotoxicity experiments, it is found that the lubricating network has good biocompatibility. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 Schematic diagram of the preparation of an epoxy resin polyrotaxane network lubricating material.

[0035] Figure 2 The differential scanning calorimetry curves of the polymer networks prepared in Example 2 and Comparative Example 2 are shown in FIG.

[0036] Figure 3 2 is a stress-strain curve diagram of the polymer network prepared in Example 2 and Comparative Example 2.

[0037] Figure 4 The mechanical properties diagram of the polymer network prepared in Example 2 and Comparative Example 2.

[0038] Figure 5 It is a dynamic friction coefficient curve of medical titanium alloy (Ti) and the polymer network prepared in Examples 1 to 3 and Comparative Examples 1 to 3.

[0039] Figure 6 It is a bar graph of the average friction coefficient of medical titanium alloy (Ti) and the polymer network prepared in Examples 1 to 3 and Comparative Examples 1 to 3, and the test conditions are 2N load and 1Hz frequency.

[0040] Figure 7 This is a graph showing the lubrication performance of medical titanium alloy (Ti) and the polymer network prepared in Examples 1 to 3 and Comparative Examples 1 to 3 under 10N load and 2Hz frequency conditions.

[0041] Figure 8 This is a graph showing the lubrication performance of medical titanium alloy (Ti) and the polymer networks prepared in Examples 1 to 3 and Comparative Examples 1 to 3 under 1N load and 2Hz frequency conditions.

[0042] Fig. 9 This is a graph showing the lubrication performance of medical titanium alloy (Ti) and the polymer network prepared in Examples 1 to 3 and Comparative Examples 1 to 3 under 5N load and 2Hz frequency conditions.

[0043] Fig.10 This is a graph showing the lubrication performance of medical titanium alloy (Ti) and the polymer network prepared in Examples 1 to 3 and Comparative Examples 1 to 3 under 5N load and 5Hz frequency conditions.

[0044] Fig.11 It is a bar graph of the wear rate of medical titanium alloy (Ti) and the polymer network prepared in Examples 1 to 3 and Comparative Examples 1 to 3.

[0045] Fig.12 This is a diagram of the lubrication performance of medical titanium alloy (Ti) and epoxy resin polyrotaxane lubrication network with different PR2000 contents under 2N load and 1Hz frequency conditions.

[0046] Fig.13 The cytotoxicity graphs of medical titanium alloy (Ti), epoxy resin without polyrotaxane (NOPR), and the polymer networks prepared in Example 2 and Comparative Example 2.

[0047] Fig.14 The cytotoxicity graphs of the polymer networks prepared in Examples 1 and 3 and Comparative Examples 1 and 3. DETAILED DESCRIPTION

[0048] The present invention will be further described below in conjunction with the accompanying drawings and specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and are not used to limit the scope of the present invention.

[0049] Example 1

[0050] Schematic diagram of the preparation of epoxy resin polyrotaxane network lubricating material Figure 1 shown.

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

[0052] Example 2

[0053] Schematic diagram of the preparation of epoxy resin polyrotaxane lubrication network Figure 1 shown.

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

[0055] According to the above process, the amount of cyclodextrin polyethylene glycol pseudopolyrotaxane PR2000 was changed to 0.0335g, 0.0675g, and 0.101g, respectively, to obtain epoxy resin polyrotaxane lubricated networks MIB-2-0.5%, MIB-2-1.0%, and MIB-2-1.5%, respectively.

[0056] Example 3

[0057] Schematic diagram of the preparation of epoxy resin polyrotaxane lubrication network Figure 1 shown.

[0058] Bisphenol A diglycidyl ether (3.4g, 10.0mmol), cyclodextrin polyethylene glycol pseudopolyrotaxane (0.135g, PR5000) and polyetheramine D400 (2.0g, 5mmol) were mixed in a 50mL plastic bottle, wherein the cyclodextrin in the cyclodextrin polyethylene glycol pseudopolyrotaxane PR5000 was α-cyclodextrin, the end group of polyethylene glycol was carboxyl, the number average molecular weight of polyethylene glycol was 5000g / mol, and the molar ratio of polyethylene glycol to cyclodextrin was 1:10. After being mixed evenly by a homogenizer, the epoxy resin prepolymer was transferred to a polytetrafluoroethylene mold, and placed in an oven at 80-100°C for reaction for 6 hours to obtain a transparent epoxy resin polyrotaxane lubricated 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 pseudo-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 polymer network Control-1 without rotaxane.

[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 pseudo-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 polymer network Control-2 without rotaxane.

[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 pseudo-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) to prepare a polymer network Control-3 without rotaxane.

[0065] Sample analysis

[0066] The polymer networks prepared in Example 2 and Comparative Example 2 were subjected to performance tests; Figure 2 The differential scanning calorimetry curves of the polymer networks prepared in Example 2 and Comparative Example 2 show that the glass transition temperature (T g ) slightly increased, indicating that the aggregation effect and hydrogen bonding produced by cyclodextrin increased the cross-linking density of the polymer network; Figure 3 The stress-strain curves of the polymer networks obtained in Example 2 and Comparative Example 2 show that the rigidity of the entire polymer is increased after the addition of the pseudopolyrotaxane of cyclodextrin polyethylene glycol; Figure 4 This is a bar chart of the mechanical properties of the polymer networks prepared in Example 2 and Comparative Example 2. It can be seen from the figure that the maximum breaking strength and Young's modulus of the polymer network increase after the addition of cyclodextrin polyethylene glycol pseudopolyrotaxane, which also indicates that the rigidity of the entire polymer network is increasing.

[0067] Figure 5 and Figure 6 The friction reduction performance diagram of the polymer network prepared in Examples 1 to 3 and Comparative Examples 1 to 3 shows that the friction coefficient (COF) of the polymer network is reduced after adding the pseudo-polyrotaxane of cyclodextrin polyethylene glycol, indicating that the polyrotaxane produces a rolling friction effect under the condition of friction force, so that it has good friction reduction performance; Figure 7-Figure 10 The lubrication performance diagrams of Examples 1 to 3 and Comparative Examples 1 to 3 under different friction conditions (load and frequency) are shown. It can be seen that with the increase of load and frequency, the lubrication performance of the examples is improved, indicating that under this condition, the rolling effect of cyclodextrin is favorable, so that the friction coefficient of the examples is lower. Fig.11 The anti-wear performance diagram of the polymer network prepared in Examples 1 to 3 and Comparative Examples 1 to 3 shows that the wear rate of the polymer network is reduced after adding the pseudo-polyrotaxane of cyclodextrin polyethylene glycol; Fig.12 This is the lubrication performance diagram of the epoxy resin polyrotaxane lubrication network at different PR2000 addition concentrations. It can be seen that the epoxy resin polyrotaxane lubrication network exhibits good lubricity at low PR2000 addition levels. Fig.13 and Fig.14 The cytotoxicity graphs of the polymer networks prepared in Examples 1 to 3 show that there is no obvious cell death in the polymer networks after the addition of cyclodextrin polyethylene glycol pseudopolyrotaxane, indicating that the polymer lubricating material has good biocompatibility.

[0068] In addition, it should be understood that after reading the above description of the present invention, those skilled in the art may make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the claims attached to this application.

Claims

1. An epoxy resin polyrotaxane network lubricating material, characterized in that: The epoxy resin polyrotaxane network lubricating material is obtained by ring-opening and curing reaction of a pseudo-polyrotaxane of polyethylene glycol and cyclodextrin, an epoxy resin monomer and a curing agent polyetheramine; In the pseudopolyrotaxane of polyethylene glycol and cyclodextrin, the molar ratio of polyethylene glycol to cyclodextrin is 1 to 100:1 to 2000, preferably 1:2 to 10, and more preferably 1:5; The molar ratio of the epoxy resin monomer, the curing agent polyetheramine, the polyethylene glycol and the pseudopolyrotaxane of cyclodextrin is 100-2000:50-1000:0.1-200.

2. The epoxy resin polyrotaxane network lubricating material according to claim 1, characterized in that: The number average molecular weight of the pseudopolyrotaxane of polyethylene glycol and cyclodextrin is 1000 to 500000 g / mol; In the pseudopolyrotaxane of polyethylene glycol and cyclodextrin, the number average molecular weight of polyethylene glycol is 600 to 5000 g / mol, preferably 600 to 2000 g / mol.

3. The epoxy resin polyrotaxane network lubricating material 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 epoxy resin polyrotaxane network lubricating material 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 epoxy resin polyrotaxane network lubricating material according to claim 1, characterized in that: Curing reaction conditions: temperature 0-180°C, time 2-72 hours.

6. The epoxy resin polyrotaxane network lubricating material according to claim 1, characterized in that: The cyclodextrin is at least one of α-cyclodextrin, β-cyclodextrin and γ-cyclodextrin.

7. The epoxy resin polyrotaxane network lubricating material according to claim 1, characterized in that: The end-capping groups of the polyethylene glycol are one or more of hydroxyl, amino, thiol and carboxyl groups.

8. The epoxy resin polyrotaxane network lubricating material according to claim 1, characterized in that: The pseudopolyrotaxane of polyethylene glycol and cyclodextrin is formed by subject-guest recognition between polyethylene glycol and cyclodextrin in water.

9. The method for preparing the epoxy resin polyrotaxane network lubricating material according to any one of claims 1 to 8, characterized in that: The epoxy resin polyrotaxane network lubricating material is obtained by subjecting the pseudo-polyrotaxane of polyethylene glycol and cyclodextrin to ring-opening and curing reactions with epoxy resin monomers and curing agent polyetheramine.

10. Use of the epoxy resin polyrotaxane network lubricating material according to any one of claims 1 to 8 in the preparation of biological lubricating materials.

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