CN118023091B - Preparation method and application of high-strength self-lubricating composite hydrogel coating - Google Patents
Preparation method and application of high-strength self-lubricating composite hydrogel coating Download PDFInfo
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Abstract
The invention relates to a preparation method and application of a high-strength self-lubricating composite hydrogel coating, which belongs to the technical field of labor protection protective materials. Then soaking water, then strengthening by using strengthening bath, purifying by using soaking water to remove redundant ions in the hydrogel coating, then dissociating the surface of the coating by using Na 2CO3 solution, finally soaking water again and cleaning to obtain the super-lubricated and durable composite hydrogel coating, and further obtaining the latex glove with the composite hydrogel coating. The composite hydrogel coating prepared by the invention has high bearing capacity and low modulus surface, excellent mechanical strength and lubricating property, and wide application prospect in the field of implantation of labor protection materials.
Description
Technical Field
The invention belongs to the technical field of labor protection materials, and particularly relates to a preparation method and application of a high-strength self-lubricating composite hydrogel coating.
Background
At present, a common problem exists in natural latex gloves, namely that the natural latex gloves have self-adhesiveness and are difficult to wear. Thus, for consumer comfort, it is desirable to treat the glove surface so that the glove can slide over the dry skin surface without significant obstruction or friction.
The existing treatment mode is to coat a layer of coating on the surface of the glove made of natural latex so as to achieve lubrication and isolation and prevent mutual adhesion. Powder coating and chlorination are widely used methods to obtain good coating properties, while polymer coatings are also used in practice, but with limited coverage.
Talcum powder is used as a lubricant coating in the early stage, but the talcum powder can fall off with dust in the use process, so that pollution is caused in the production and use processes, allergic reaction to some people is also possible, and the use of the powder latex gloves is gradually reduced.
With the limitations of powder coated gloves, the more established traditional approach is chlorination, which is also a method of enhancing the degree of lubrication. Chlorine gas or sodium hypochlorite is generally adopted in the industry to treat the glove in the production process of the natural rubber glove, the surface of the glove after chlorination treatment is smooth, the glove is convenient to wear, and the adhesion in the production and storage of the glove is solved. However, the method releases chlorine in the preparation process, which causes environmental pollution; in addition, the chlorination, turn-over and drying processes are added in the production, so that continuous production can not be realized; finally, the production control requirements are strict, otherwise, excessive halogenation of rubber is caused, the mechanical properties of the glove are reduced, the material is possibly embrittled, unpleasant smell is generated, and the color change problem is caused.
In recent years, manufacturers adopt polyacrylate emulsion to coat natural latex gloves to produce powder-free gloves, but the defects of delamination, poor biocompatibility and the like during stretching exist.
Lubricating hydrogel coatings are of interest to many researchers due to their good drag reducing properties. However, due to the complexity of the practical use environment, in designing a lubricious hydrogel coating, it should be considered to enhance various properties of the coating in terms of durability in addition to making its drag reducing performance as good as possible. For example, a lubricious hydrogel coating that can withstand high loads can withstand greater pressures without failing, maintaining its performance and appearance under greater loads.
Disclosure of Invention
The invention aims to provide a preparation method and application of a high-strength self-lubricating composite hydrogel coating.
In order to solve the technical problems, the invention adopts the following technical scheme: the preparation method of the high-strength self-lubricating composite hydrogel coating comprises the following steps:
s1, scraping a viscous epoxy precursor solution on a substrate by means of a glass rod, and pre-curing for 1-2 hours at 50-70 ℃ to form a semi-cured epoxy resin layer;
The epoxy resin layer cured for more than 1 hour exhibited high modulus, non-tacky solid state properties, but a significant amount of epoxy functionality was still present.
S2, coating a layer of modified span (surfactant) on the surface of the epoxy resin layer in a semi-cured state of the epoxy resin layer, curing for 1-3h at 50-70 ℃ to completely cure and finish surface modification at the same time to form the modified epoxy resin layer.
S3, after the modified epoxy resin layer is completely cured, cleaning and airing the modified epoxy resin layer;
The modified epoxy resin layer is washed with hot water to wash out unreacted span molecules, and finally dried, at which time the surface of the modified epoxy resin layer exhibits hydrophilic properties.
S4, coating the viscous hydrogel precursor solution on the surface of the modified epoxy resin layer, waiting for spreading and leveling, and then adding ultraviolet light to irradiate 128mW cm -2 for 2-4 hours for polymerization reaction to convert the viscous hydrogel precursor solution into a hydrogel coating;
the preparation method of the viscous hydrogel precursor solution comprises the following steps: preparing an aqueous solution containing acrylamide, N' -methylene bisacrylamide, ketoglutaric acid, carboxymethyl cellulose and sodium caseinate, mechanically stirring and uniformly mixing the aqueous solution, centrifuging at a rotating speed of 2000-4000rpm for 10-20min, and removing bubbles to form a viscous hydrogel precursor solution.
The polymerization reaction is carried out in an open environment without sealing.
S5, soaking the hydrogel coating into water, recovering the water lost in the polymerization process, transferring the hydrogel coating into a cross-linking agent solution, soaking for 2-4 hours at 50-70 ℃ to strengthen the hydrogel coating, and soaking the hydrogel coating in water again to remove the redundant cross-linking agent after strengthening;
s6, dissociating the reinforced hydrogel coating surface crosslinked sodium caseinate and Ca 2+ by using Na 2CO3 solution to form a sparse crosslinked hydrogel coating with good lubricating property;
as the multivalent counterion (Ca 2+) is detrimental to the formation of the surface hydration layer and can reduce lubricity.
S7, re-soaking the hydrogel coating in water to remove redundant Na 2CO3 and some unstable solid substances on the surface of the hydrogel, and finally forming the composite hydrogel coating with super-strong lubricity.
Further, in step S1, the preparation method of the viscous epoxy precursor solution is as follows: e-51 epoxy resin and 650 polyamide curing agent are added into a beaker according to the proportion of 1:1 to 1:1.3, and stirred for 10-30min to form viscous epoxy precursor solution.
Further, titanium dioxide (TiO 2) was additionally introduced as a white pigment to whiten the E-51 epoxy resin, the titanium dioxide being added in an amount corresponding to 7-10wt% of the total amount of the E-51 epoxy resin and 650 polyamide curing agent. The white pigment in the epoxy resin layer can reflect more ultraviolet light in the subsequent photopolymerization process of the hydrogel coating, so that the utilization rate of the ultraviolet light is improved.
Further, in step S2, the preparation method of the modified span includes: mixing Span20 and glycidyl methacrylate at a mixing ratio of 10:1, and reacting at 40-50 ℃ for 4-6h.
Further, in step S4, 2mol/L of acrylamide, 1mmol/L of N, N' -methylenebisacrylamide, 1mmol/L of ketoglutaric acid, 3wt% of carboxymethyl cellulose and 3wt% of sodium caseinate were included in the aqueous solution.
Further, in step S5, the hydrogel coating is soaked in deionized water for 2-4min, so that the water lost in the polymerization process is recovered. Then, the mixture is placed into a strengthening bath for soaking for 2 to 4 hours to form chemical crosslinking and physical crosslinking among sodium caseinate molecules, wherein the strengthening bath comprises a mixed solution of CaCl 2 with the concentration of 1mol/L and sorbitol with the concentration of 0.5 percent v/v, and the reaction temperature is 50 to 70 ℃. Then, the hydrogel coating is soaked in a large amount of water again, and redundant molecules and ions in the hydrogel coating are removed.
Further, in the step S6, the coordination of Ca 2+ and sodium caseinate on the surface of the hydrogel coating after the dissociation strengthening is carried out by using 0.25 mol/L Na 2CO3 solution, and the dissociation time is 8-12min.
Another object of the present invention is to provide a composite hydrogel coating obtained by the above preparation method.
It is another object of the present invention to provide the use of the above-described preparation method for preparing a composite hydrogel-coated latex glove.
Furthermore, on the basis of the existing latex glove production process, the latex glove with the latex coating is taken as a base material, and the composite hydrogel coating is coated on the latex glove through the preparation method.
The beneficial effects of the invention are as follows:
The invention constructs a multi-layer structure composite hydrogel coating, which takes hydrogel as a main body, is fixed on a base material (latex glove) by means of epoxy resin, and not only ensures that the coating shows super-strong lubricity, but also solves the problem that the existing hydrogel is not durable by designing the structure of the hydrogel.
The preparation method comprises the steps of taking adhesive epoxy precursor solution as primer directly coated on a base material (latex glove), coating modified span in a semi-dry state of an epoxy resin layer, completely curing, cleaning and airing, pouring adhesive hydrogel precursor solution, waiting for leveling of the adhesive hydrogel precursor solution, then carrying out ultraviolet irradiation, and loading a hydrogel coating on the epoxy resin layer. Followed by a series of post-treatment steps: firstly soaking water, then reinforcing the hydrogel coating by using a reinforcing bath, then soaking water to purify and remove redundant ions in the hydrogel coating, then dissociating the surface of the coating by using Na 2CO3 solution, and finally soaking water again to clean, thus obtaining the super-lubricated and durable composite hydrogel coating (or latex glove with the composite hydrogel coating).
The main body of the composite hydrogel coating contains rich caseinate-calcium ion dynamic crosslinking points, and the composite hydrogel coating shows enough rebound resilience under the repeated action of external force, so that the composite hydrogel coating is stable in long-term use; while the polymer chains of the surface remain chemically crosslinked, so that lubricity is well maintained after long-term storage.
The composite hydrogel coating has softness and smooth feeling, is not easy to fall off after being put on a latex glove, has good elasticity, lubricity and luster, has certain hydrophilicity, can adsorb a certain amount of sweat, is comfortable to wear, and is not easy to generate peculiar smell and irritation caused by sweat.
In conclusion, the preparation method is easy to implement, mild in reaction condition, good in safety and convenient for large-scale production, and the prepared composite hydrogel coating has high bearing capacity and low-modulus surface, has excellent mechanical strength and lubricating property, and has wide application prospect in the field of implantation of labor protection materials.
Detailed Description
The present invention will be described in further detail with reference to preferred embodiments, so that those skilled in the art can better understand the technical aspects of the present invention.
The preparation method of the high-strength self-lubricating composite hydrogel coating comprises the following steps:
s1, scraping a viscous epoxy precursor solution on a substrate by means of a glass rod, and pre-curing for 1-2 hours at 60 ℃ to form a semi-cured epoxy resin layer;
The epoxy resin layer cured for more than 1 hour exhibited high modulus, non-tacky solid state properties, but a significant amount of epoxy functionality was still present.
S2, coating a layer of modified span (surfactant) on the surface of the epoxy resin layer in a semi-cured state of the epoxy resin layer, curing for 2 hours at 60 ℃, completely curing and simultaneously finishing surface modification to form the modified epoxy resin layer.
S3, after the modified epoxy resin layer is completely cured, cleaning and airing the modified epoxy resin layer;
The modified epoxy resin layer is washed with hot water to wash out unreacted span molecules, and finally dried, at which time the surface of the modified epoxy resin layer exhibits hydrophilic properties.
S4, coating the viscous hydrogel precursor solution on the surface of the modified epoxy resin layer, waiting for spreading and leveling, and then carrying out polymerization reaction by ultraviolet light irradiation of 128mW cm -2 for 3 hours to convert the viscous hydrogel precursor solution into a hydrogel coating;
The preparation method of the viscous hydrogel precursor solution comprises the following steps: preparing an aqueous solution containing 2mol/L acrylamide, 1mmol/L N, N' -methylenebisacrylamide, 1mmol/L ketoglutaric acid, 3wt% of carboxymethyl cellulose and 3wt% of sodium caseinate, mechanically stirring and uniformly mixing the aqueous solution, and centrifuging at 3000rpm for 15min to remove bubbles and form a viscous hydrogel precursor solution.
The polymerization reaction is carried out in an open environment without sealing.
S5, soaking the hydrogel coating into water, recovering the water lost in the polymerization process, transferring the hydrogel coating into a cross-linking agent solution, soaking for 3 hours at the temperature of 60 ℃ to strengthen the hydrogel coating, and soaking the hydrogel coating in water again to remove the redundant cross-linking agent after strengthening;
s6, dissociating the reinforced hydrogel coating surface crosslinked sodium caseinate and Ca 2+ by using Na 2CO3 solution to form a sparse crosslinked hydrogel coating with good lubricating property;
as the multivalent counterion (Ca 2+) is detrimental to the formation of the surface hydration layer and can reduce lubricity.
S7, re-soaking the hydrogel coating in water to remove redundant Na 2CO3 and some unstable solid substances on the surface of the hydrogel, and finally forming the composite hydrogel coating with super-strong lubricity.
In step S1, the preparation method of the viscous epoxy precursor solution is as follows: e-51 epoxy resin and 650 polyamide curing agent are added into a beaker according to the proportion of 1:1 to 1:1.3, and stirred for 20min to form viscous epoxy precursor solution.
In addition, titanium dioxide (TiO 2) was additionally introduced as a white pigment to whiten the E-51 epoxy resin, the titanium dioxide being added in an amount corresponding to 7-10wt% of the total amount of E-51 epoxy resin and 650 polyamide curing agent. The white pigment in the epoxy resin layer can reflect more ultraviolet light in the subsequent photopolymerization process of the hydrogel coating, so that the utilization rate of the ultraviolet light is improved.
In the step S2, the preparation method of the modified span comprises the following steps: mixing Span20 and glycidyl methacrylate at a mixing ratio of 10:1, wherein the reaction condition is that the temperature is 45 ℃ and the time is 5 hours.
In step S5, the hydrogel coating is immersed in deionized water for 3 minutes to recover the water lost during the polymerization. Then, the mixture is placed in a strengthening bath for soaking for 3 hours, so that chemical crosslinking and physical crosslinking are formed among sodium caseinate molecules, wherein the strengthening bath comprises a mixed solution of CaCl 2 with the concentration of 1mol/L and sorbitol with the concentration of 0.5% v/v, and the reaction temperature is 60 ℃. Then, the hydrogel coating is soaked in a large amount of water again, and redundant molecules and ions in the hydrogel coating are removed.
In step S6, the coordination of Ca 2+ and sodium caseinate on the surface of the reinforced hydrogel coating is dissociated by using 0.25mol/L Na 2CO3 solution, and the dissociation time is 10min.
Another object of the present invention is to provide a composite hydrogel coating obtained by the above preparation method.
It is another object of the present invention to provide the use of the above-described preparation method for preparing a composite hydrogel-coated latex glove.
Based on the existing latex glove production process, the latex glove with the latex coating is used as a base material, and the composite hydrogel coating is coated on the latex glove through the preparation method.
In combination with the prior art, the production procedures of the hydrogel coating latex glove are as follows: dipping coagulant, drying, dipping latex, curling, leaching, preparing composite hydrogel coating and demolding.
The ultra-high lubricity composite hydrogel coating prepared in the above example was used for the following test.
Characterization of mechanical properties of the ultra-high lubricity composite hydrogel coating:
This example characterizes the mechanical properties and resilience of the hydrogel portion of the composite hydrogel coating. The hydrogel as a whole can bear high-strength compressive stress of 18.2MPa (at 90% strain) and is not broken, and the compressive toughness (area of a hysteresis loop) can reach 1.2 MJ.m -3. The rigid hydrogel layer below the top hydration layer is interpenetrated with a polyacrylamide network and a sodium caseinate network to form an interpenetrating double-network structure, physical and chemical crosslinking exists among polymer chains, and the molecular chains have both flexible and rigid fragments, so that the hydrogel has high mechanical strength.
In addition, this example performed a series of load-unload cycles to measure the self-restorative properties of the hydrogels. Taking 30 cycles as an example, cycle 1 has significantly higher strength and greater hysteresis than the next 30 cycles, but the strength and toughness exhibited by the subsequent cycles gradually stabilize. It can be seen that some brittle structures undergo permanent dissociation in the first cycle, while the hydrogel structure gradually tends to be dynamically balanced in subsequent cycles, with reversible structural damage and recovery. In these compression cycles, the stress and dissipation energy of the compression cycles gradually stabilize as the number of compression cycles increases, and in particular after the 15 th cycle, the hysteresis loops overlap, which indicates that the mechanical properties of the hydrogel exhibit properties similar to those of an elastomer. The hydrogel after repeated compression can be obtained to have excellent self-recovery and anti-fatigue characteristics, and the ionic crosslinked network has a large number of dynamic physical crosslinks and can be destroyed and rebuilt under the action of external force.
Characterization and analysis of lubricating performance of a composite hydrogel coating with super-strong lubricating performance:
1. Rotational friction test:
lubricity is the primary property of the composite hydrogel coating, which in this example is characterized by tribological testing of the composite hydrogel coating by a ball-and-disc tribometer. The spherical friction probe contacts with the composite hydrogel coating under water, and the composite hydrogel coating is subjected to a rotary friction test.
As the load increases from 1N to 5N, the coefficient of friction of the composite hydrogel coating at different normal forces increases from 0.013 to 0.021, always at an ultra-low level. As the load increases to 20N, the coefficient of friction increases to 0.053, also exhibiting some degree of lubricity. Even at the lowest load of 1N, the contact stress reached 408kPa, while the contact stress at 20N load was 1705kPa. Thus, it is believed that the composite hydrogel coating overcomes the disadvantage of not being able to withstand large loads. In addition, the composite hydrogel coating also has different friction coefficients under the action of different sliding frequencies, the composite hydrogel coating has excellent lubricating performance under all sliding frequencies from 0.5Hz to 7Hz, and the friction coefficient mu value is different from 0.012 to 0.026. In addition, the composite hydrogel coating has excellent lubricating performance on different materials. The composite hydrogel coating exhibits different coefficients of friction for different types of materials. All materials of the probe can show ultra-low friction coefficient of 0.013 to 0.021 when sliding on the composite hydrogel coating. However, the substrate with the composite hydrogel coating exhibited very significant drag reducing effects relative to the substrate without the composite hydrogel coating, and the large difference in coefficient of friction reflected the significant drag reducing effects of the lubricating coating. Finally, a long-distance friction test of 3km was also performed. The result shows that the friction coefficient is stabilized at about 0.017, and the composite hydrogel coating has stable performance in the long-term use process.
2. Linear friction test:
The composite hydrogel coating exhibits an ultra-low coefficient of friction of from 0.014 to 0.025 under a load of 1N to 10N. Even though the sliding friction coefficient was increased to 0.052 under a load of 20N, lubricity was still exhibited to some extent. As normal stress increases, the sliding friction coefficient decreases and then increases. When the normal force is 4N, the corresponding contact stress is 783kPa, which is the optimal condition for representing the lubricity of the composite hydrogel coating. The contact stress is as high as 1217kPa under a load of 10N, but the lubricity (μ=0.024) is still excellent in this state. In addition, the composite hydrogel coating exhibits a sliding coefficient of friction that varies from 0.014 to 0.022 when the sliding frequency is from 0.5Hz to 7Hz under normal force 4N. Compared with the base material without the composite hydrogel coating, the composite hydrogel coating has remarkable drag reduction effect, and compared with the base material, the composite hydrogel coating has more than 90 percent of drag reduction effect. Finally, a 3km friction test was also performed, in which the relative sliding friction coefficient gradually decreased from 0.024 to 0.018 and tended to stabilize, probably due to the probe rubbing against the composite hydrogel coating, causing some degree of polishing of the sample. The results show that the lubricating property of the super-lubricating composite hydrogel coating has strong bearing capacity and durability when the tribology test is operated under various conditions.
The foregoing describes the embodiments of the present invention in detail, but the description is only a preferred embodiment of the present invention and should not be construed as limiting the scope of the invention. All equivalent changes and modifications within the scope of the present invention are intended to be covered by this patent.
Claims (9)
1. A preparation method of a high-strength self-lubricating composite hydrogel coating is characterized by comprising the following steps of: the method comprises the following steps:
S1, scraping adhesive epoxy precursor solution on a substrate by means of a glass rod to form a semi-cured epoxy resin layer;
S2, coating a layer of modified span on the surface of the epoxy resin layer in a semi-cured state of the epoxy resin layer, and completely curing and finishing the surface modification to form a modified epoxy resin layer;
s3, cleaning and airing the modified epoxy resin layer;
S4, coating the viscous hydrogel precursor solution on the surface of the modified epoxy resin layer, waiting for spreading and leveling, and then carrying out polymerization reaction by ultraviolet irradiation to convert the viscous hydrogel precursor solution into a hydrogel coating;
The preparation method of the viscous hydrogel precursor solution comprises the following steps: preparing an aqueous solution containing acrylamide, N' -methylene bisacrylamide, ketoglutaric acid, carboxymethyl cellulose and sodium caseinate, mechanically stirring and uniformly mixing the aqueous solution, and removing bubbles to form a viscous hydrogel precursor solution;
s5, soaking the hydrogel coating into water, transferring the hydrogel coating into a cross-linking agent solution for soaking to strengthen the hydrogel coating, and re-soaking the hydrogel coating into water for soaking after strengthening to remove the redundant cross-linking agent;
S6, dissociating the reinforced hydrogel coating surface crosslinked sodium caseinate and Ca 2+ by using Na 2CO3 solution to form a sparse crosslinked hydrogel coating;
s7, re-soaking the hydrogel coating in water to form a composite hydrogel coating with super-strong lubricity;
In step S1, the preparation method of the viscous epoxy precursor solution is as follows: e-51 epoxy resin and 650 polyamide curing agent are added into a beaker according to the proportion of 1:1 to 1:1.3, and a viscous epoxy precursor solution is formed after stirring.
2. The method for preparing the high-strength self-lubricating composite hydrogel coating according to claim 1, which is characterized in that: titanium dioxide is introduced into the viscous epoxy precursor solution, and the addition amount of the titanium dioxide is 7-10wt% of the total amount of the E-51 epoxy resin and the 650 polyamide curing agent.
3. The method for preparing the high-strength self-lubricating composite hydrogel coating according to claim 1, which is characterized in that: in the step S2, the preparation method of the modified span comprises the following steps: mixing Span20 and glycidyl methacrylate at a mixing ratio of 10:1, and reacting at 40-50 ℃ for 4-6h.
4. The method for preparing the high-strength self-lubricating composite hydrogel coating according to claim 1, which is characterized in that: in step S4, the aqueous solution contains 2mol/L acrylamide, 1mmol/L N, N' -methylenebisacrylamide, 1mmol/L ketoglutaric acid, 3wt% carboxymethylcellulose and 3wt% sodium caseinate.
5. The method for preparing the high-strength self-lubricating composite hydrogel coating according to claim 1, which is characterized in that: in step S5, the hydrogel coating is soaked in deionized water for 2-4min, then placed in a strengthening bath for soaking for 2-4h, wherein the strengthening bath comprises a mixed solution of CaCl 2 with the concentration of 1mol/L and sorbitol with the concentration of 0.5% v/v, the reaction temperature is 50-70 ℃, and then the hydrogel coating is soaked in a large amount of water.
6. The method for preparing the high-strength self-lubricating composite hydrogel coating according to claim 1, which is characterized in that: in the step S6, the coordination of Ca 2+ and sodium caseinate on the surface of the hydrogel coating after the reinforcement is dissociated by using 0.25mol/L Na 2CO3 solution, and the dissociation time is 8-12min.
7. A composite hydrogel coating obtainable by the method of preparing a high strength self-lubricating composite hydrogel coating according to any one of claims 1 to 6.
8. Use of a method for preparing a high strength self-lubricating composite hydrogel coating according to any one of claims 1 to 6 for preparing a composite hydrogel coating latex glove.
9. The use according to claim 8, characterized in that: the latex glove with the latex coating is used as a base material, and the composite hydrogel coating is coated on the latex glove through a preparation method of the composite hydrogel coating.
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