Low-hydrogen deproteinized latex medical surgical gloves and preparation method thereof

Abstract

The invention discloses low-hydrogen deproteinized latex medical surgical gloves and a preparation method. The low-hydrogen deproteinized latex medical surgical gloves are prepared from deproteinized natural concentrated latex, an L-arginine-zinc complex aqueous solution, urocanic acid ethyl ester, HNTs-PEG, ZnO, an accelerant, sulfur and an anti-aging agent. The HNTs-PEG, the L-arginine-zinc complex aqueous solution and the ethyl urocanate are added in the process of preparing the latex gloves, a complexing-covalent network interpenetrating structure is constructed, a protein network removed from natural latex is replaced, the strength and toughness loss caused by the protein network is made up, and the latex gloves have the advantages of being good in stability and good in stability. Meanwhile, the L-arginine-zinc complex replaces traditional ammonia water to serve as a stabilizer, low-hydrogen treatment is achieved, and the prepared low-hydrogen deproteinized latex gloves are good in biocompatibility and low in sensitization, have a tiny scratch self-repairing function and can be used in the field of medical treatment and public health.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of medical gloves, in particular to a low-hydrogen deproteinized latex medical surgical glove and a preparation method thereof. BACKGROUND

[0002] Natural Rubber Latex (NRL) has long been the core of high-performance medical surgical glove manufacturing due to its unparalleled elasticity, toughness and tactile feedback. However, as a biosynthetic material, its two inherent defects have severely restricted its application and development in modern medical environments. First, the multiple proteins it contains can trigger type I hypersensitivity reactions, posing a serious occupational health threat to long-term exposed medical staff. Second, traditional NRL processing relies on high-concentration ammonia as a preservative, which not only pollutes the production environment and harms workers' health, but also may remain in the final product, causing potential irritation to users.

[0003] Therefore, developing a new generation of medical latex gloves with both deproteinization and low-ammonia / ammonia-free characteristics has become a frontier focus and urgent need in the fields of material science and biomedical engineering worldwide. Currently, cutting-edge research is working to reduce allergenic protein content to a minimum through enzymatic hydrolysis-centrifugation complex processes, and exploring the use of green and mild preservative systems such as amino acid salts, new surfactants, etc. to replace ammonia water, in order to eradicate the two major hidden dangers of type I hypersensitivity and chemical irritation from the source. However, in the natural latex system, protein molecules are not simply impurities, they are adsorbed on the surface of rubber particles, forming a crucial biological interface network. This network not only gives the latex excellent colloidal stability, but also, after vulcanization into a film, as a natural reinforcing phase, greatly improves the material's toughness and tear strength. When this layer of protein network is removed by enzymatic hydrolysis, etc., the mechanical properties of the latex product will drop sharply, becoming fragile and vulnerable, unable to meet the stringent safety requirements of surgical operations. At the same time, compared to high-ammonia systems, traditional low-ammonia or ammonia-free preservative systems usually have weaker ability to stabilize the latex, making the stability of the deproteinized latex system further decline, bringing great challenges to storage and processing.

[0004] In the prior art, CN117511010B uses cellulose nanocrystals as a reinforcing material, mainly to address the problem of decreased mechanical properties after deproteinization. It compensates for the strength loss by introducing high-strength nanofillers. However, this is usually done within a relatively mature or traditional latex stabilization system, without fully considering its complex compatibility with novel low-ammonia / ammonia-free stabilizers. In the prior art, CN118290828B uses a modified diatomaceous earth scheme to construct a stable ammonia-free system, utilizing the porous structure and surface properties of diatomaceous earth to assist in stabilizing the latex. However, its effect as a reinforcing agent is limited and cannot completely replace the unique role of the protein network in toughening and tear resistance.

[0005] Therefore, developing a novel latex system that can not only effectively replace the removed protein network and compensate for the resulting loss of strength and toughness, but also be highly compatible with low-ammonia / ammonia-free preservation systems is a problem that urgently needs to be solved in this field. Summary of the Invention

[0006] In view of the shortcomings of the prior art, the present invention discloses a low-hydrogen deproteinized latex medical surgical glove and its preparation method, the details of which are as follows.

[0007] This invention protects a low-hydrogen deproteinized latex medical surgical glove, comprising 100 parts of deproteinized natural concentrated latex, 1-2 parts of an aqueous solution of L-arginine-zinc complex, 2-4 parts of ethyl urethane, 1-3 parts of HNTs-PEG, 0.5-1 parts of ZnO, 0.5-0.7 parts of an accelerator, 1.5-2 parts of sulfur, and 1-1.5 parts of an antioxidant; The deproteinized natural concentrated latex has a solid content of 60%. The HNTs-PEG is prepared by modifying halloysite nanotube powder with amino activation and then reacting it with mPEG-NHS.

[0008] Preferably, the low-hydrogen deproteinized latex medical surgical glove comprises 100 parts of deproteinized natural concentrated latex, 1 part of an aqueous solution of L-arginine-zinc complex, 3 parts of ethyl urethane, 2 parts of HNTs-PEG, 1 part of ZnO, 0.5 parts of accelerator, 1.5 parts of sulfur, and 1 part of antioxidant.

[0009] Preferably, the HNTs-PEG is prepared by the following method: Step 1: Disperse halloysite nanotube powder in toluene, add 3-aminopropylethoxysilane, reflux at 80°C for 12 h under nitrogen protection, centrifuge, wash the precipitate three times alternately with toluene and ethanol, and dry under vacuum at 60°C for 8 h to obtain HNTs-NH2 powder. Step two, disperse HNTs-NH2 powder in DMF to obtain HNTs-NH2 suspension, dissolve mPEG-NHS with molecular weight of 2000 Da in DMF, drop into HNTs-NH2 suspension, react at 25℃ for 24h, centrifugal, precipitate is washed with deionized water for 3 times, dialysis using dialysis bag with molecular weight cut-off of 10000 Da, freeze-drying to obtain HNTs-PEG powder.

[0010] Preferably, the mass ratio of the halloysite nanotube powder and 3-aminopropyl ethoxysilane is 8-10:1.

[0011] Preferably, the mass ratio of the HNTs-NH2 powder and mPEG-NHS is 2:1.

[0012] Preferably, the L-arginine-zinc complex aqueous solution is prepared by the following method: dissolving L-arginine powder in deionized water, adding zinc salt solution dropwise, stirring at 150 rpm at 50℃ for 30 min, rotary evaporation to a zinc ion concentration of 0.5 M to obtain an L-arginine-zinc complex aqueous solution.

[0013] Preferably, the molar ratio of L-arginine in the L-arginine powder to zinc ions in the zinc salt solution is 2:1.

[0014] Preferably, the zinc salt solution is a zinc sulfate solution or a zinc acetate solution.

[0015] The application also protects a preparation method of the above low hydrogen deproteinized latex medical surgical glove, comprising the following steps: mixing deproteinized natural concentrated latex and L-arginine-zinc complex aqueous solution at 25℃, stirring at 150 rpm for 2h, adding ethyl urocanate and mixing uniformly, reacting at 40℃ for 1h, adding HNTs-PEG, ZnO, accelerator ZDBC, sulfur and antioxidant 4010NA, mixing uniformly to obtain a rubber compound, immersing a hand mold into a coagulant, taking it out and immersing it into the rubber compound after aging, taking it out and draining, vulcanizing, demolding to obtain a low hydrogen deproteinized latex medical surgical glove. The coagulant is a 20wt% calcium nitrate solution or a 20wt% calcium chloride solution.

[0016] Preferably, the vulcanization is divided into two stages, the first stage has a temperature of 90℃ and a time of 15 min; the second stage has a temperature of 115℃ and a time of 10 min.

[0017] The application has the following beneficial effects: The present application constructs a complex-covalent network interpenetrating structure by adding HNTs-PEG, L-arginine-zinc complex aqueous solution and ethyl urocanate in the process of preparing latex gloves, replaces the protein network removed in natural latex, makes up for the loss of strength and toughness caused thereby, and replaces traditional ammonia as a stabilizer with L-arginine-zinc complex, realizes low hydrogen treatment, and the prepared low-hydrogen deproteinized latex gloves have good biocompatibility and low allergenicity, and can be used in the field of medical health.

[0018] (1) In the preparation of HNTs-PEG, halloysite nanotubes are an aluminosilicate, and the surface is rich in hydroxyl groups. The ethoxyl groups on the surface of 3-aminopropyl ethoxysilane undergo dehydration condensation reaction under heating conditions to generate stable Si-O-Al / Si covalent bonds, so as to modify the amino group to the surface of halloysite nanotubes; the NHS ester group at the end of mPEG-NHS can undergo nucleophilic substitution reaction with the amino group on the surface of HNTs-NH2 to form a stable amide bond, so as to graft the PEG segment to the surface of HNTs-NH2. The PEG segment has a large number of ether oxygen bonds and hydroxyl groups, has strong hydrophilicity, and greatly improves the uniformity of halloysite nanotubes in rubber; the halloysite structure in the prepared HNTs-PEG enhances the strength of the latex gloves, and the ether oxygen bonds on the PEG segment can coordinate with zinc ions to promote the generation of subsequent complex network structure.

[0019] (2) The present application mixes deproteinized natural concentrated latex with L-arginine-zinc complex aqueous solution, uses non-volatile and non-irritating L-arginine-zinc complex to replace traditional ammonia as a stabilizer, reduces the hydrogen content and odor residue of the latex gloves; the zinc ions in the L-arginine-zinc complex are introduced into the rubber system in the form of a stable and slow-release complex in advance, avoiding the problem of uneven dispersion caused by subsequent direct addition of zinc oxide, which causes local instability of the latex structure; the guanidino group in L-arginine-zinc complex has strong alkalinity in aqueous solution, which can effectively maintain the required negative charge on the surface of the latex particles, prevent particle aggregation through electrostatic repulsion, and thus enhance the dispersion uniformity and colloidal stability of the latex.

[0020] (3) In the curing process of preparing the latex gloves, the L-arginine-zinc complex and zinc oxide will release free zinc ions under mild heating conditions at 35-40℃. These zinc ions, as Lewis acids, will coordinate with the imidazole ring and carboxyl group of ethyl urocanate on the surface of adjacent rubber to form a stable complex structure, connecting the originally independent rubber particles to form a weak crosslinking network structure, thereby enhancing the strength and thickness uniformity of the wet gel film in the subsequent leaching process. The hand mold can bring up a more uniform gel film during leaching, and the probability of sagging and edge shrinking is reduced.

[0021] (4) In the first stage of the vulcanization process, the temperature is first raised to 90-95 DEG C, under the action of the accelerator ZDBC, the sulfur and the polyisoprene in the rubber are subjected to a rapid crosslinking reaction to form a permanent polysulfide covalent network, at the same time, the ethyl urocanate is subjected to a diene addition reaction with the rubber main chain to form a covalent bond, at this temperature, the ion bond breaking and recombination rate is accelerated, the complex network structure formed by the ethyl urocanate and zinc ions has a certain fluidity, thereby effectively releasing the internal stress generated by the covalent bond formation. In the second stage, the temperature is raised to 110-115 DEG C, the crosslinking density is further increased, so that the vulcanization reaction and the diene addition reaction are more complete, forming a complete polysulfide covalent network, at this temperature, the ion bond breaking and recombination rate is greatly accelerated, so that the complex network structure formed by the ethyl urocanate and zinc ions is rapidly dissociated and recombined in the already fixed polysulfide covalent network, thereby forming a stable complex-covalent network interpenetrating structure, enhancing the tensile properties and elongation at break of the latex glove. When the latex glove is subjected to external force stretching or impact, the energy will be preferentially absorbed by the ion bond in the complex network which has a relatively weak strength, the ion bond breaks and recombines, thereby protecting the covalent network as the skeleton from being damaged, increasing the toughness, tear resistance and service life of the latex glove; when the latex glove has a small scratch, the rubber covalent network at the broken part is damaged, but the ethyl urocanate thereon will re-form an ionic bond with the surrounding zinc ions at room temperature, thereby realizing self-repairing of the latex glove, further prolonging the service life and safety of the latex glove. BRIEF DESCRIPTION OF DRAWINGS

[0022] Figure 1 The preparation method flowchart of the low-hydrogen deproteinized latex medical surgical glove of the present application is shown. DETAILED DESCRIPTION

[0023] The technical solutions of the present application will be described clearly and completely below in conjunction with the embodiments, obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0024] The mPEG-NHS used in the embodiments of the present application is derived from Shanghai Pingsuo Biological Technology Co., Ltd., the CAS is 756525-94-7, the Chinese name is methoxy PEG active ester, the article number is PS1-H-2K, and the molecular weight is 2000; the halloysite nanotube powder used is derived from Jiangsu Xianfeng Nanometer Material Technology Co., Ltd., the article number is 103763, and the CAS is 1332-58-7; the ethyl urocanate used is derived from Shaanxi Laido New Material Co., Ltd., the CAS is 27538-35-8, and the purity is 98%.

[0025] The application prepares a low-hydrogen deproteinized latex medical surgical glove, which comprises deproteinized natural concentrated latex 100 parts, L-arginine-zinc complex aqueous solution 1-2 parts, ethyl urocanate 2-4 parts, HNTs-PEG 1-3 parts, ZnO 0.5-1 part, accelerator 0.5-0.7 part, sulfur 1.5-2 parts and anti-aging agent 1-1.5 parts; The solid content of the deproteinized natural concentrated latex is 60%. The HNTs-PEG is prepared by modifying halloysite nanotube powder through amino activation and then reacting with mPEG-NHS.

[0026] In an embodiment of the application, the low-hydrogen deproteinized latex medical surgical glove comprises deproteinized natural concentrated latex 100 parts, L-arginine-zinc complex aqueous solution 1 part, ethyl urocanate 3 parts, HNTs-PEG 2 parts, ZnO 1 part, accelerator 0.5 part, sulfur 1.5 parts and anti-aging agent 1 part.

[0027] In an embodiment of the application, the HNTs-PEG is prepared by the following method: Step one, disperse halloysite nanotube powder in toluene, add 3-aminopropyl ethoxysilane, reflux at 80 DEG C under nitrogen protection for 12 hours, centrifuge, wash the precipitate with toluene and ethanol alternately for 3 times, and dry at 60 DEG C under vacuum for 8 hours to obtain HNTs-NH2 powder; Step two, disperse HNTs-NH2 powder in DMF to obtain HNTs-NH2 suspension, dissolve mPEG-NHS with a molecular weight of 2000 Da in DMF, drop into the HNTs-NH2 suspension, react at 25 DEG C for 24 hours, centrifuge, wash the precipitate with deionized water for 3 times, dialysis using a dialysis bag with a molecular weight cut-off of 10000 Da, freeze-dry to obtain HNTs-PEG powder.

[0028] It can be understood that in the embodiment of the application, halloysite nanotube is an aluminosilicate, and the surface is rich in hydroxyl groups. The ethoxyl group on the surface of 3-aminopropyl ethoxysilane and the hydroxyl group on the surface of halloysite nanotube perform dehydration condensation reaction under heating condition to generate stable Si-O-Al / Si covalent bond, so that the amino group is modified to the surface of halloysite nanotube. The NHS ester group at the end of mPEG-NHS can perform nucleophilic substitution reaction with the amino group on the surface of HNTs-NH2 to form stable amide bond, so that the PEG segment is grafted to the surface of HNTs-NH2.

[0029] In an embodiment of the application, the mass ratio of the halloysite nanotube powder and 3-aminopropyl ethoxysilane is 8-10:1.

[0030] In one embodiment of this application, the mass ratio of the HNTs-NH2 powder to mPEG-NHS is 2:1.

[0031] In one embodiment of this application, the L-arginine-zinc complex aqueous solution is prepared by the following method: L-arginine powder is dissolved in deionized water, zinc salt solution is added dropwise, the mixture is stirred at 50°C and 150 rpm for 30 min, and then rotary evaporated until the zinc ion concentration is 0.5 M to obtain the L-arginine-zinc complex aqueous solution.

[0032] In one embodiment of this application, the molar ratio of L-arginine in the L-arginine powder to zinc ions in the zinc salt solution is 2:1.

[0033] It is understood that, in the embodiments of this application, by adding zinc salt solution to L-arginine aqueous solution, zinc ions undergo a complexation reaction with the amino and carboxyl groups of L-arginine to form coordinate bonds, thereby generating L-arginine-zinc complex.

[0034] In one embodiment of this application, the zinc salt solution is a zinc sulfate solution or a zinc acetate solution.

[0035] like Figure 1 As shown, one embodiment of this application also discloses a method for preparing the above-mentioned low-hydrogen deproteinized latex medical surgical gloves, including the following steps: at 25°C, deproteinized natural concentrated latex and an aqueous solution of L-arginine-zinc complex are mixed and stirred at 150 rpm for 2 hours. A propylene glycol solution of ethyl urethane is added and mixed evenly. The mixture is reacted at 40°C for 1 hour. HNTs-PEG, ZnO, accelerator ZDBC, sulfur and antioxidant 4010NA are added and mixed evenly to obtain a rubber compound. The rubber compound is stirred at 30-50 rpm for 12-24 hours at 35-40°C for curing. The hand mold is immersed in a coagulant, removed and then immersed in the cured rubber compound. After removal and draining, the mixture is vulcanized and demolded to obtain low-hydrogen deproteinized latex medical surgical gloves. The coagulant is a 20wt% calcium nitrate solution or a 20wt% calcium chloride solution.

[0036] It can be understood that, in the embodiment of the application, by mixing the deproteinized natural concentrated latex with the L-arginine-zinc complex aqueous solution, the L-arginine-zinc complex without volatile and irritating odor is used to replace the traditional ammonia as the stabilizer, thereby reducing the hydrogen content and odor residue of the latex glove; the zinc ion of the L-arginine-zinc complex is introduced into the rubber system in advance in the form of a stable and slow-release complex, thereby avoiding the problem of uneven dispersion caused by subsequent direct addition of zinc oxide, and the problem of local instability of the latex caused by the uneven dispersion; the guanidine group in the arginine in the L-arginine-zinc complex has strong alkalinity in the aqueous solution, and can effectively maintain the required negative charge on the surface of the latex particles, thereby preventing the particles from gathering through electrostatic repulsion, and thereby enhancing the dispersion uniformity and colloidal stability of the latex.

[0037] It can be understood that, in the embodiment of the application, the ethyl urocanate is fixed on the surface of the rubber by adding the propylene glycol solution of the ethyl urocanate during the latex mixing process. Propylene glycol is a biocompatible solvent, and has a slight swelling effect on polyisoprene in the rubber. When the propylene glycol solution of the ethyl urocanate is added, the propylene glycol will carry the ethyl urocanate to penetrate into the surface layer of the rubber due to the swelling effect. Affected by the van der Waals force, the propylene glycol gradually disperses into the water phase, and the hydrophobic ethyl urocanate stays on the surface of the rubber.

[0038] It can be understood that, in the embodiment of the application, during the curing process, the L-arginine-zinc complex and zinc oxide release free zinc ions under the condition of mild heating at 35-40℃. The zinc ions act as Lewis acids and coordinate with the imidazole ring and carboxyl group of the ethyl urocanate on the surface of the adjacent rubber to form a stable complex structure, thereby connecting the originally independent rubber particles to form a weak crosslinking network structure, and thereby enhancing the thickness uniformity of the wet gel film in the subsequent leaching process.

[0039] It can be understood that, in the embodiment of the application, during the hand mold leaching process, the calcium ions in the coagulant can quickly neutralize the charge on the surface of the negatively charged rubber particles, destroy the colloidal stability, and cause irreversible aggregation of the rubber particles on the surface of the hand mold to form a wet gel film.

[0040] In an embodiment of the application, the vulcanization is divided into two stages, the temperature of the first stage is 90-95℃, and the time is 15 min; the temperature of the second stage is 110-115℃, and the time is 10 min.

[0041] It can be understood that, in the embodiment of the present application, in the first stage of the vulcanization process, the temperature is first raised to 90-95℃, under the action of the accelerator ZDBC, the sulfur and the polyisoprene in the rubber undergo a rapid crosslinking reaction to form a permanent covalent network of polysulfide bonds, at the same time, the ethyl urocanate undergoes a diene addition reaction with the main chain of the rubber to form a covalent bond, at this temperature, the rate of ionic bond breaking and recombination is accelerated, the complex network structure formed by the ethyl urocanate and zinc ions has a certain fluidity, thereby effectively releasing the internal stress generated by the covalent bond formation. In the second stage, the temperature is raised to 110-115℃, the crosslinking density is further increased, so that the vulcanization reaction and the diene addition reaction proceed more completely, forming a complete covalent network of polysulfide bonds, at this temperature, the rate of ionic bond breaking and recombination is greatly accelerated, so that the complex network structure formed by the ethyl urocanate and zinc ions rapidly dissociates and recombines in the already fixed covalent network of polysulfide bonds, thereby forming a stable complex-covalent network interpenetrating structure.

[0042] Example 1 In this embodiment, a low-hydrogen deproteinized latex medical surgical glove is prepared, which comprises deproteinized natural concentrated latex 100 parts, L-arginine-zinc complex aqueous solution 1 part, ethyl urocanate 3 parts, HNTs-PEG 2 parts, ZnO 1 part, accelerator 0.5 part, sulfur 1.5 parts and antioxidant 1 part. In this embodiment, the solid content of the deproteinized natural concentrated latex is 60%. In this embodiment, the HNTs-PEG is prepared by the following method: Step one, disperse the halloysite nanotube powder in toluene, add 3-aminopropyl ethoxysilane, reflux at 80℃ for 12h under nitrogen protection, centrifuge, wash the precipitate with toluene and ethanol alternately for 3 times, and dry at 60℃ under vacuum for 8h to obtain HNTs-NH2 powder; Step two, disperse the HNTs-NH2 powder in DMF to obtain a HNTs-NH2 suspension, dissolve mPEG-NHS with a molecular weight of 2000Da in DMF, drop it into the HNTs-NH2 suspension, and react at 25℃ for 24h, centrifuge, wash the precipitate with deionized water for 3 times, dialysis using a dialysis bag with a molecular weight cut-off of 10000Da, freeze-drying to obtain HNTs-PEG powder.

[0043] In this embodiment, the mass ratio of the halloysite nanotube powder and 3-aminopropyl ethoxysilane is 10:1.

[0044] In this embodiment, the mass ratio of the HNTs-NH2 powder and mPEG-NHS is 2:1.

[0045] In the present embodiment, the L-arginine-zinc complex aqueous solution is prepared by the following method: dissolving L-arginine powder in deionized water, adding a zinc salt solution dropwise, stirring at 150 rpm at 50℃ for 30 min, and rotary evaporation to a zinc ion concentration of 0.5M to obtain the L-arginine-zinc complex aqueous solution.

[0046] In the present embodiment, the molar ratio of L-arginine in the L-arginine powder to zinc ions in the zinc salt solution is 2:1.

[0047] In the present embodiment, the zinc salt solution is a zinc sulfate solution.

[0048] The preparation method of the low-hydrogen deproteinized latex medical surgical glove of the present embodiment comprises the following steps: mixing deproteinized natural concentrated latex and L-arginine-zinc complex aqueous solution at 25℃, stirring at 150 rpm for 2h, adding ethyl urocanate propylene glycol solution and mixing uniformly, reacting at 40℃ for 1h, adding HNTs-PEG, ZnO, accelerator ZDBC, sulfur and antioxidant 4010NA, mixing uniformly to obtain a rubber compound, aging the rubber compound at 40℃ with stirring at 50 rpm for 24h, selecting a ceramic hand mold and preheating it to 70℃, immersing it in a 20wt% calcium nitrate solution for 10s, drying it at 60℃ for 1min, then immersing it in the aged rubber compound, leaving it for 15s, taking it out and draining it at 25℃ for 30s, then heating it at 90℃ for 15min, then heating it at 115℃ for 10min, washing it in deionized water at 90℃ for 2min, peeling the glove off the hand mold, and obtaining the low-hydrogen deproteinized latex medical surgical glove.

[0049] Example 2 A low-hydrogen deproteinized latex medical surgical glove is prepared in the present embodiment, which comprises deproteinized natural concentrated latex 100 parts, L-arginine-zinc complex aqueous solution 2 parts, ethyl urocanate 4 parts, HNTs-PEG 3 parts, ZnO 0.5 parts, accelerator 0.7 parts, sulfur 2 parts and antioxidant 1.5 parts. The solid content of the deproteinized natural concentrated latex is 60%. In the present embodiment, the low-hydrogen deproteinized latex medical surgical glove comprises deproteinized natural concentrated latex 100 parts, L-arginine-zinc complex aqueous solution 1 part, ethyl urocanate 3 parts, HNTs-PEG 2 parts, ZnO 1 part, accelerator 0.5 part, sulfur 1.5 part and antioxidant 1 part.

[0050] In the present embodiment, the HNTs-PEG is prepared by the following method: Step one, disperse the halloysite nanotube powder in toluene, add 3-aminopropyl ethoxysilane, reflux at 80℃ for 12h under nitrogen protection, centrifugal, precipitate is washed with toluene and ethanol alternately for 3 times, vacuum drying at 60℃ for 8h, to obtain HNTs-NH2 powder; Step two, disperse the HNTs-NH2 powder in DMF to obtain HNTs-NH2 suspension, dissolve mPEG-NHS with molecular weight of 2000Da in DMF, drop into the HNTs-NH2 suspension, react at 25℃ for 24h, centrifugal, precipitate is washed with deionized water for 3 times, dialysis using dialysis bag with molecular weight cut-off of 10000Da, freeze-drying to obtain HNTs-PEG powder.

[0051] In this embodiment, the mass ratio of the halloysite nanotube powder and 3-aminopropyl ethoxysilane is 8:1.

[0052] In this embodiment, the mass ratio of the HNTs-NH2 powder and mPEG-NHS is 2:1.

[0053] In this embodiment, the L-arginine-zinc complex aqueous solution is prepared by the following method: dissolve L-arginine powder in deionized water, drop in zinc salt solution, stir at 150rpm for 30min at 50℃, rotary evaporation to zinc ion concentration of 0.5M to obtain L-arginine-zinc complex aqueous solution.

[0054] In this embodiment, the molar ratio of L-arginine in the L-arginine powder and zinc ion in the zinc salt solution is 2:1.

[0055] In this embodiment, the zinc salt solution is zinc acetate solution.

[0056] The preparation method of the low hydrogen deproteinized latex medical surgical glove of this embodiment comprises the following steps: mix the deproteinized natural concentrated latex and the L-arginine-zinc complex aqueous solution at 25℃, stir at 150rpm for 2h, add the propylene glycol solution of urocanic acid ethyl ester and mix uniformly, react at 40℃ for 1h, add HNTs-PEG, ZnO, accelerator ZDBC, sulfur and antioxidant 4010NA and mix uniformly to obtain the rubber compound, age the rubber compound at 35℃ by stirring at 30rpm for 20h, select a ceramic hand mold and preheat to 70℃, immerse in a calcium chloride solution with a concentration of 20wt% for 10s, take out and dry at 60℃ for 1min, then immerse in the aged rubber compound, stay for 15s, take out and drain at 25℃ for 30s, then heat at 95℃ for 15min, heat at 115℃ for 10min, wash in deionized water at 90℃ for 2min, peel off the glove from the hand mold to obtain the low hydrogen deproteinized latex medical surgical glove.

[0057] Example 3 In this example, a low-hydrogen deproteinized latex medical surgical glove is prepared, which comprises deproteinized natural concentrated latex 100 parts, L-arginine-zinc complex aqueous solution 1 part, ethyl urocanate 2 parts, HNTs-PEG 2 parts, ZnO 1 part, accelerator 0.5 part, sulfur 1.5 parts and antioxidant 1.5 parts. In this example, the solid content of the deproteinized natural concentrated latex is 60%. In this example, the low-hydrogen deproteinized latex medical surgical glove comprises deproteinized natural concentrated latex 100 parts, L-arginine-zinc complex aqueous solution 1 part, ethyl urocanate 3 parts, HNTs-PEG 2 parts, ZnO 1 part, accelerator 0.5 part, sulfur 1.5 parts and antioxidant 1 part.

[0058] In this example, the HNTs-PEG is prepared by the following method: Step one, disperse halloysite nanotube powder in toluene, add 3-aminopropyl ethoxysilane, reflux at 80°C for 12h under nitrogen protection, centrifuge, precipitate is washed with toluene and ethanol alternately for 3 times, vacuum dried at 60°C for 8h to obtain HNTs-NH2 powder; Step two, disperse HNTs-NH2 powder in DMF to obtain HNTs-NH2 suspension, dissolve mPEG-NHS with molecular weight of 2000Da in DMF, drop into HNTs-NH2 suspension, react at 25°C for 24h, centrifuge, precipitate is washed with deionized water for 3 times, dialysis using dialysis bag with molecular weight cut-off of 10000Da, freeze-drying to obtain HNTs-PEG powder.

[0059] In this example, the mass ratio of halloysite nanotube powder and 3-aminopropyl ethoxysilane is 8-10:1.

[0060] In this example, the mass ratio of HNTs-NH2 powder and mPEG-NHS is 2:1.

[0061] In this example, the L-arginine-zinc complex aqueous solution is prepared by the following method: dissolve L-arginine powder in deionized water, drop zinc salt solution, stir at 150rpm for 30min at 50°C, rotary evaporation to zinc ion concentration of 0.5M to obtain L-arginine-zinc complex aqueous solution.

[0062] In this example, the molar ratio of L-arginine in L-arginine powder and zinc ion in zinc salt solution is 2:1.

[0063] In this example, the zinc salt solution is zinc sulfate solution.

[0064] The preparation method of the low-hydrogen deproteinized latex medical surgical glove of the embodiment comprises the following steps: mixing deproteinized natural concentrated latex and an aqueous solution of L-arginine-zinc complex at 25℃, stirring at a speed of 150 rpm for 2h, adding an ethyl propiolate propylene glycol solution and mixing uniformly, reacting at 40℃ for 1h, adding HNTs-PEG, ZnO, accelerator ZDBC, sulfur and antioxidant 4010NA, mixing uniformly to obtain a rubber compound, aging the rubber compound at 40℃ by stirring at a speed of 50 rpm for 12h, selecting a ceramic hand mold and preheating it to 60℃, immersing it in a 20wt% calcium nitrate solution for 5s, drying it at 60℃ for 1min after taking it out, then immersing it in the aged rubber compound for 10s, taking it out and draining it at 25℃ for 30s, then heating it at 90℃ for 15min and at 110℃ for 10min, washing it in deionized water at 90℃ for 2min, peeling the glove from the hand mold, and obtaining the low-hydrogen deproteinized latex medical surgical glove.

[0065] Comparative Example 1 In the preparation method of the low-hydrogen deproteinized latex medical surgical glove of the present comparative example, an equal amount of halloysite nanotube powder was used to replace HNTs-PEG, and the rest was the same as in Example 1.

[0066] Comparative Example 2 In the preparation method of the low-hydrogen deproteinized latex medical surgical glove of the present comparative example, an equal amount of aqueous solution was used to replace the aqueous solution of L-arginine-zinc complex, and the rest was the same as in Example 1.

[0067] Comparative Example 3 In the preparation method of the low-hydrogen deproteinized latex medical surgical glove of the present comparative example, an equal amount of propylene glycol was used to replace the ethyl propiolate propylene glycol solution, and the rest was the same as in Example 1.

[0068] Comparative Example 4 The non-deproteinized glove was selected from the medical protective brand Ansell Gammex® Latex series medical surgical gloves.

[0069] The latex gloves of Examples 1-3 and Comparative Examples 1-4 were subjected to mechanical property testing, and the test results are shown in Table 1 below:

[0070] As can be seen from Table 1, compared with the common non-deproteinized latex gloves on the market, the tensile properties of the gloves of the embodiments are close, and the elongation at break is improved, indicating that the complex-covalent interpenetrating network structure of the latex gloves prepared in the embodiments has good tear resistance. The latex gloves of Example 2 have the largest amount of the aqueous solution of L-arginine-zinc complex, ethyl urocanate and HNTs-PEG, so the mechanical properties are the best in the example group; Comparative Example 1 does not modify the halloysite nanotube powder, resulting in a decrease in the dispersion uniformity of the halloysite nanotube powder in the latex, a substantial decrease in the tensile strength and a decrease in the elongation at break; in Comparative Example 2, the lack of L-arginine-zinc complex results in the inability to pre-disperse zinc ions in the latex, and the lack of the addition of a stabilizer in the latex results in uneven dispersion of the components in the system, leading to a substantial decrease in the mechanical properties; Comparative Example 3 does not add ethyl urocanate, which cannot form a covalent bond with the rubber main body through diene polymerization, so the complex network and the covalent network in the latex system do not form an interpenetrating network structure, and the mechanical properties of the latex gloves are less affected.

[0071] Although the embodiments of the present application have been shown and described, it is to be understood that various changes, modifications, substitutions and variations can be made in these embodiments without departing from the principles and spirit of the present application, and any equivalent changes and improvements made within the scope of the present application should still fall within the scope of the present patent.

Claims

1. A low-hydrogen deproteinized latex medical surgical glove characterized in that, The composition comprises 100 parts of deproteinized natural concentrated latex, 1-2 parts of L-arginine-zinc complex aqueous solution, 2-4 parts of ethyl urocanate, 1-3 parts of HNTs-PEG, 0.5-1 part of ZnO, 0.5-0.7 part of accelerator, 1.5-2 parts of sulfur and 1-1.5 parts of antioxidant; The solid content of the deproteinized natural concentrated latex is 60%. The HNTs-PEG is prepared by modifying halloysite nanotube powder through amino activation and then reacting with mPEG-NHS.

2. The low hydrogen deproteinized latex medical surgical glove according to claim 1, wherein, The composition comprises 100 parts of deproteinized natural concentrated latex, 1 part of L-arginine-zinc complex aqueous solution, 3 parts of ethyl urocanate, 2 parts of HNTs-PEG, 1 part of ZnO, 0.5 part of accelerator, 1.5 parts of sulfur and 1 part of antioxidant.

3. The low hydrogen deproteinized latex medical surgical glove according to claim 1, wherein, The HNTs-PEG is prepared by the following method: Step one: halloysite nanotube powder is dispersed in toluene, 3-aminopropyl ethoxysilane is added, and the mixture is refluxed at 80°C for 12 hours under nitrogen protection, then centrifuged, the precipitate is washed with toluene and ethanol alternately for 3 times, and dried at 60°C under vacuum for 8 hours to obtain HNTs-NH2 powder; Step two: HNTs-NH2 powder is dispersed in DMF to obtain HNTs-NH2 suspension, mPEG-NHS with a molecular weight of 2000 Da is dissolved in DMF and added dropwise into the HNTs-NH2 suspension, and the mixture is reacted at 25°C for 24 hours, then centrifuged, the precipitate is washed with deionized water for 3 times, dialyzed using a dialysis bag with a molecular weight cut-off of 10000 Da, and freeze-dried to obtain HNTs-PEG powder.

4. The low hydrogen deproteinized latex medical surgical glove according to claim 3, characterized in that, The mass ratio of the halloysite nanotube powder to 3-aminopropyl ethoxysilane is 8-10:

1.

5. The low hydrogen deproteinized latex medical surgical glove according to claim 3, wherein, The mass ratio of the HNTs-NH2 powder to mPEG-NHS is 2:

1.

6. The low hydrogen deproteinized latex medical surgical glove of claim 1, wherein, The L-arginine-zinc complex aqueous solution is prepared by the following method: L-arginine powder is dissolved in deionized water, and zinc salt solution is added dropwise, the mixture is stirred at 50°C at a rotation speed of 150 rpm for 30 minutes, and then rotary evaporated to a zinc ion concentration of 0.5M to obtain the L-arginine-zinc complex aqueous solution.

7. The low hydrogen deproteinized latex medical surgical glove according to claim 6, wherein, The molar ratio of L-arginine in the L-arginine powder to zinc ions in the zinc salt solution is 2:

1.

8. The low hydrogen deproteinized latex medical surgical glove according to claim 6, wherein, The zinc salt solution is zinc sulfate solution or zinc acetate solution.

9. A process for the preparation of a low hydrogen deproteinized latex medical surgical glove as claimed in any one of claims 1 to 8, characterized in that, The method comprises the following steps: mixing deproteinized natural concentrated latex and L-arginine-zinc complex aqueous solution at 25°C, stirring at a rotation speed of 150 rpm for 2 hours, adding ethyl urocanate and mixing uniformly, reacting at 40°C for 1 hour, adding HNTs-PEG, ZnO, accelerator ZDBC, sulfur and antioxidant 4010NA and mixing uniformly to obtain a rubber compound, immersing a hand mold into a coagulant, taking out and immersing into the rubber compound after aging, taking out and draining, vulcanizing, demolding to obtain low-hydrogen deproteinized latex medical surgical gloves. The coagulant is 20wt% calcium nitrate solution or 20wt% calcium chloride solution.

10. The method of claim 9, wherein, The vulcanization is divided into two stages, the first stage has a temperature of 90-95 DEG C and a time of 15 min, and the second stage has a temperature of 110-115 DEG C and a time of 10 min.

Images