Low-ammonia latex medical examination glove and preparation method thereof

Abstract

The invention belongs to the technical field of medical gloves, and particularly relates to a low-ammonia latex medical inspection glove and a preparation method thereof.The low-ammonia latex medical inspection glove is prepared from, by weight, 100 parts of concentrated natural latex, 5-15 parts of high-thermal-conductivity silicon dioxide, 1-2.5 parts of vulcanizing agent, 0.5-1.5 parts of zinc oxide, 0.5-1.5 parts of accelerant, 1-2 parts of antioxidant and 0.1-0.5 part of surfactant; the preparation method of the high-thermal-conductivity silicon dioxide comprises the following steps: preparing mercapto silane coupling agent modified porous silicon dioxide, then soaking and adding the porous silicon dioxide into a mixed solution of a silver ammonia solution and an isoprene-vinyl alcohol copolymer, and then adding a reducing agent and an initiator for in-situ reduction deposition of silver and copolymer grafting to obtain the high-thermal-conductivity silicon dioxide. Silver is deposited on the surface and in pores of porous silicon dioxide, the thermal conductivity of silicon dioxide is improved, then the thermal conductivity of the latex gloves is improved, and meanwhile the strength of the latex gloves is improved through grafting modification of the isoprene-vinyl alcohol copolymer.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of medical gloves, and particularly relates to a low-ammonia latex medical examination glove and a preparation method thereof. BACKGROUND

[0002] Medical gloves, as indispensable protective equipment in medical scenarios, are widely used in various medical activities such as clinical diagnosis and treatment, surgical operation, nursing service, etc. The core function of medical gloves is to establish a physical barrier to isolate the hands of medical staff from the body fluids, secretions and pathogenic microorganisms of patients, thereby protecting medical staff from infection risk and preventing cross infection. With the development of medical technology, higher requirements are put forward for the comprehensive performance of medical gloves. In addition to meeting the basic protection needs, the flexibility of operation, the comfort of wearing and the durability of use should also be considered. Among them, the strength reliability and sweat adaptability are the key performance indicators that affect the actual use effect of gloves.

[0003] Although natural rubber gloves have good elasticity and fit, they are prone to breakage and tearing when subjected to external forces such as stretching, friction and puncture during complex medical operations. For example, repeated friction between instruments and gloves during surgery may cause damage to the fingertips or palm of the gloves. The stretching action during patient transfer and medical consumable arrangement during nursing may cause cracking at the joint of the gloves. Insufficient strength of the gloves not only leads to failure of the protective barrier, causing cross infection, but also affects the operation precision due to glove damage, delays the medical process, and even causes medical accidents.

[0004] In addition, when medical staff wear gloves for a long time, the heat generated by hand metabolism cannot be effectively dissipated, and the air permeability between the glove and the skin is poor, so sweat easily accumulates inside the glove, forming a humid and hot microenvironment. This situation brings multiple problems: first, the accumulation of sweat increases the friction between the skin of the hand and the inner wall of the glove, affecting the flexibility of operation and possibly causing the glove to slip off, especially during delicate operations such as surgical suturing and instrument holding, glove slippage may cause serious medical risks; second, long-term humid environment easily causes the skin of the hand to become white and wrinkled, damaging the skin barrier function and increasing the probability of contact dermatitis for medical staff. Some people with allergic constitution may also aggravate allergic reactions due to the interaction between sweat and glove material. In the prior art, solutions to the problem of sweating are mostly focused on improving the air permeability of the glove material, such as using porous structure design or adding air-permeable fibers. However, such designs often sacrifice the sealing performance and strength of the glove, making it difficult to balance between protection performance, strength and air permeability. Some gloves use silicone oil or other lubricants to reduce friction by coating the inner wall, but the lubricant is easy to fall off, the long-term use effect is not good, and it may pollute the medical operation environment.

[0005] In summary, the existing medical gloves still have significant deficiencies in strength reliability and sweat adaptability. Therefore, developing a medical glove that takes into account high strength, anti-breakage performance and good sweat adaptability, solving the performance short board of existing products, has important significance for improving medical operation safety, protecting the health of medical staff and optimizing medical service quality, and has become a technical problem to be solved in the field. SUMMARY

[0006] The purpose of the present application is to provide a low ammonia latex medical examination glove and its preparation method, by depositing silver on the surface and pores of porous silica, improving the thermal conductivity of silica, and further improving the thermal conductivity of latex gloves, and by grafting modification of isoprene-vinyl alcohol copolymer to improve the strength of latex gloves.

[0007] To achieve the above-mentioned purpose, the present application provides a low ammonia latex medical examination glove, the raw materials of which include, by weight: concentrated natural latex 100 parts, high thermal conductivity silica 5-15 parts, vulcanizing agent 1-2.5 parts, zinc oxide 0.5-1.5 parts, accelerator 0.5-1.5 parts, antioxidant 1-2 parts and surfactant 0.1-0.5 parts. The preparation method of the high thermal conductivity silica includes: preparing mercapto silane coupling agent modified porous silica, then immersing and adding into a mixed solution composed of silver ammonia solution and isoprene-vinyl alcohol copolymer, then adding reducing agent and free radical initiator for in-situ reduction and deposition of silver and grafting of copolymer, to obtain high thermal conductivity silica.

[0008] Further, the preparation of the isoprene-vinyl alcohol copolymer includes: obtaining isoprene and vinyl acetate copolymer by emulsion polymerization of isoprene and vinyl acetate, then adding alkali to obtain isoprene-vinyl alcohol copolymer.

[0009] Further, the molar ratio of isoprene and vinyl acetate is 1:(1-3), and the molecular weight of isoprene-vinyl alcohol copolymer is 2000-8000.

[0010] Further, the mass ratio of isoprene-vinyl alcohol copolymer to silver in silver ammonia solution is (0.2-0.6):1.

[0011] Further, the preparation of the mercapto silane coupling agent modified porous silica includes: adding tetraethyl orthosilicate to a mixed solution of water and ethanol containing cetyltrimethylammonium bromide, then adding hydrochloric acid to control the pH value to 2-4, and performing hydrolysis and condensation reaction, after the reaction is completed, calcining to remove cetyltrimethylammonium bromide to obtain porous silica; then modifying the porous silica with mercapto silane coupling agent to obtain mercapto silane coupling agent modified porous silica.

[0012] Further, the mercapto silane coupling agent is gamma-mercaptopropyl trimethoxysilane; and the addition amount of the mercapto silane coupling agent is 8%-18% of the mass of the porous silica.

[0013] Further, the volume ratio of the water and the ethanol is 1: (3-5) ; and the addition amount of the cetyl trimethyl ammonium bromide is 10%-15% of the tetraethyl orthosilicate. The temperature of the hydrolysis condensation reaction is 35-60 DEG C.

[0014] Further, the reducing agent is glucose, formaldehyde, hydrazine or tartaric acid; and the free radical initiator is azobisisobutyronitrile. The solid content of the concentrated natural latex is 60wt%-70wt%, and the ammonia content is ≤0.1%.

[0015] The application further provides a preparation method of the low-ammonia latex medical examination glove.

[0016] Further, the temperature of the vulcanization is 90-110 DEG C, and the time is 15-30 min.

[0017] Overall, the above technical solutions conceived by the application mainly have the following technical advantages: 1. The low-ammonia latex medical examination glove provided by the application can form a coordination bond with silver through the mercapto silane coupling agent, thereby improving the adsorption efficiency and firmness of silver ions, and thereby depositing silver in the surface and pores of the porous silica, improving the thermal conductivity of the silica, and further improving the thermal conductivity of the latex glove, which can promote the heat dissipation of the palm and reduce the sweating problem during use. At the same time, the mercapto group can also add to the isoprene-vinyl alcohol copolymer to realize the grafting of the copolymer. The copolymer can improve the moisture absorption of the glove by using the hydrophilicity of the polyvinyl alcohol segment to promote the heat dissipation, and on the other hand, the polyisoprene segment can be polymerized with the rubber molecular chain of the natural latex, thereby improving the strength.

[0018] 2. The application can comprehensively improve the mechanical properties and thermal conductivity of the glove by adjusting the ratio of the isoprene-vinyl alcohol copolymer and silver, and the molar ratio of isoprene and vinyl acetate. DETAILED DESCRIPTION

[0019] In order to make the objects, technical solutions and advantages of the present application clearer, the present application will be further described in details below with embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application and not used to limit the present application. In addition, the technical features involved in the various embodiments of the present application described below can be combined with each other as long as they do not conflict with each other.

[0020] The present application provides a low-ammonia latex medical examination glove, the raw materials of which include, by weight: concentrated natural latex 100 parts, high-thermal-conductivity silicon dioxide 5-15 parts, vulcanizing agent 1-2.5 parts, zinc oxide 0.5-1.5 parts, accelerator 0.5-1.5 parts, antioxidant 1-2 parts, and surfactant 0.1-0.5 parts. The preparation method of the high-thermal-conductivity silicon dioxide includes: preparing porous silicon dioxide modified by mercapto silane coupling agent, then immersing and adding into a mixed solution composed of silver-ammonia solution and isoprene-vinyl alcohol copolymer, then adding reducing agent and free radical initiator to carry out in-situ reduction deposition of silver and grafting of the copolymer, to obtain high-thermal-conductivity silicon dioxide.

[0021] In this way, the mercapto silane coupling agent can form a coordination bond with silver, improving the adsorption efficiency and firmness of silver ions, so as to deposit silver in the surface and pores of the porous silicon dioxide, improving the thermal conductivity of the silicon dioxide, and further improving the thermal conductivity of the latex glove, which can promote the heat dissipation of the palm and reduce the sweating problem during use. At the same time, the mercapto group can also react with the isoprene-vinyl alcohol copolymer to realize grafting of the copolymer. The copolymer can improve the moisture absorption of the glove by using the hydrophilicity of the polyvinyl alcohol segment to promote the heat dissipation, and on the other hand, the polyisoprene segment can polymerize with the rubber molecular chain of the natural latex to improve the strength.

[0022] Further, the preparation of the isoprene-vinyl alcohol copolymer includes: obtaining isoprene-vinyl acetate copolymer by emulsion polymerization of isoprene and vinyl acetate, and then hydrolyzing with alkali to obtain isoprene-vinyl alcohol copolymer.

[0023] Further, the molar ratio of isoprene and vinyl acetate is 1: (1-3), and the molecular weight of the isoprene-vinyl alcohol copolymer is 2000-8000. By adjusting the proportion of the isoprene-vinyl alcohol segment, the moisture absorption and strength can be balanced, and the toughness of the glove can be prevented from being reduced due to excessive crosslinking.

[0024] Further, the mass ratio of the isoprene-vinyl alcohol copolymer and silver in the silver ammine solution is (0.2-0.6):1. By adjusting the mass ratio, while ensuring the moisture absorption, strength and thermal conductivity, the silver ammine solution is prevented from being too little to form a thermal conduction network, or too much to cover the isoprene-vinyl alcohol copolymer on the graft, so as to make it difficult to improve the moisture absorption and strength.

[0025] Further, the preparation of the mercapto silane coupling agent modified porous silica includes: adding tetraethyl orthosilicate into a mixed solution of water and ethanol containing cetyltrimethylammonium bromide, then adding hydrochloric acid to control the pH value to 2-4, and performing a hydrolysis condensation reaction, and after the reaction is completed, calcining to remove the cetyltrimethylammonium bromide to obtain the porous silica; and then modifying the porous silica with a mercapto silane coupling agent to obtain the mercapto silane coupling agent modified porous silica.

[0026] Further, the mercapto silane coupling agent is γ-mercaptopropyl trimethoxysilane; and the addition amount of the mercapto silane coupling agent is 8%-18% of the mass of the porous silica.

[0027] Further, the volume ratio of the water and ethanol is 1:(3-5); and the addition amount of the cetyltrimethylammonium bromide is 10%-15% of the tetraethyl orthosilicate. The temperature of the hydrolysis condensation reaction is 35-60℃.

[0028] Further, the reducing agent is glucose, formaldehyde, hydrazine or tartaric acid; and the free radical initiator is azobisisobutyronitrile. The solid content of the concentrated natural latex is 60wt%-70wt%, and the ammonia content is ≤0.1%.

[0029] Embodiment 1 A preparation method of a micro-ammonia latex medical examination glove, comprising: adding 10 parts of high-thermal-conductivity silica, 2 parts of sulfur, 1 part of zinc oxide, 1 part of an accelerator, 1.2 parts of an antioxidant and 0.3 parts of a surfactant into 100 parts of micro-ammonia concentrated natural latex (solid content 66%), uniformly mixing, pouring into a mold, drying, vulcanizing (temperature 100℃, time 20min), to obtain the micro-ammonia latex medical examination glove.

[0030] The preparation method of the high-thermal-conductivity silica comprises: Step 1: tetraethyl orthosilicate was added to a mixed solution of water and ethanol (volume ratio of 1:4) containing cetyltrimethylammonium bromide (added amount of 12% of the tetraethyl orthosilicate), and then a hydrolysis catalyst was added, and then reacted at 45°C, and then centrifuged, washed, dried, and calcined at 550°C to remove the cetyltrimethylammonium bromide to obtain porous silica. Then the porous silica was modified with γ-mercaptopropyltrimethoxysilane (added amount of 12wt% of the porous silica) to obtain mercapto silane coupling agent modified porous silica.

[0031] Step 2: the mercapto silane coupling agent modified porous silica was added to a mixed solution of 0.3mol / L silver ammine solution and isoprene-vinyl alcohol copolymer, and then immersed and adsorbed for 2h, and then warmed to 60°C, and then added glucose and azobisisobutyronitrile, and then reacted for 1h to obtain high thermal conductivity silica. The mass ratio of the isoprene-vinyl alcohol copolymer to silver in the silver ammine solution was 0.3:1.

[0032] The preparation of the isoprene-vinyl alcohol copolymer included: isoprene and vinyl acetate in a molar ratio of 1:2 were subjected to emulsion polymerization to obtain isoprene-vinyl acetate copolymer, and then sodium hydroxide was added to hydrolyze to obtain isoprene-vinyl alcohol copolymer with a molecular weight of 5000.

[0033] Example 2 The difference from Example 1 was that the mass ratio of the isoprene-vinyl alcohol copolymer to silver in the silver ammine solution was 0.6:1.

[0034] Example 3 The difference from Example 1 was that the molar ratio of isoprene and vinyl acetate was 1:1.

[0035] Comparative Example 1 The difference from Example 1 was that no high thermal conductivity silica was added. Other than that, it was the same as Example 1.

[0036] Comparative Example 2 The difference from Example 1 was that the high thermal conductivity silica was not modified with γ-mercaptopropyltrimethoxysilane. Other than that, it was the same as Example 1.

[0037] Comparative Example 3 The difference from Example 1 was that Step 1 was: tetraethyl orthosilicate was added to a mixed solution of water and ethanol (volume ratio of 1:4), and then hydrochloric acid was added to control the pH value to 3, and then reacted at 45°C, and then centrifuged, washed, and dried to obtain silica. Then the silica was modified with mercapto silane coupling agent KH550 (added amount of 10wt% of the silica) to obtain mercapto silane coupling agent modified silica. Other than that, it was the same as Example 1, i.e. no porous structure.

[0038] The tensile properties were tested according to the test standard GB / T 528-2009.

[0039] Table 1 Performance test results of examples and comparative examples

[0040] As can be seen from Table 1, when the high-thermal-conductivity silicon dioxide prepared by the present application is added, the thermal conductivity is significantly improved compared to that without addition, and the tensile strength is excellent, and the toughness is also better. When the silicon dioxide does not have a porous structure (Comparative Example 3), the thermal conductivity decreases; when silver is not deposited and the isoprene-vinyl alcohol copolymer is not grafted (Comparative Example 1), the thermal conductivity and strength decrease significantly. When the amount of isoprene-vinyl alcohol copolymer increases compared to that of silver, the thermal conductivity decreases, the elongation at break decreases, and the elasticity is poor. When the molar ratio of isoprene and vinyl acetate increases, the thermal conductivity changes little, but the elongation at break decreases significantly. Therefore, the present application can realize the comprehensive improvement of mechanical properties and thermal conductivity by parameter optimization.

[0041] Those skilled in the art will easily understand that the above description is only the preferred embodiment of the present application, and is not intended to limit the present application, and any modification, equivalent replacement and improvement made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A low-ammonia latex medical examination glove, characterized in that, Its raw materials, by weight, include: 100 parts concentrated natural latex, 5-15 parts high thermal conductivity silica, 1-2.5 parts vulcanizing agent, 0.5-1.5 parts zinc oxide, 0.5-1.5 parts accelerator, 1-2 parts antioxidant, and 0.1-0.5 parts surfactant; The method for preparing the high thermal conductivity silica includes: preparing porous silica modified with mercaptosilane coupling agent, then impregnating it into a mixed solution composed of silver ammonia solution and isoprene-vinyl alcohol copolymer, followed by adding a reducing agent and a free radical initiator to perform in-situ reduction deposition of silver and grafting of copolymer to obtain high thermal conductivity silica.

2. The low-ammonia latex medical examination glove according to claim 1, characterized in that, The preparation of the isoprene-vinyl alcohol copolymer includes: emulsion polymerization of isoprene and vinyl acetate to obtain an isoprene-vinyl acetate copolymer, followed by alkaline hydrolysis to obtain the isoprene-vinyl alcohol copolymer.

3. The low-ammonia latex medical examination glove according to claim 2, characterized in that, The molar ratio of isoprene to vinyl acetate is 1:(1-3), and the molecular weight of the isoprene-vinyl alcohol copolymer is 2000-8000.

4. The low-ammonia latex medical examination glove according to claim 1, characterized in that, The mass ratio of isoprene-vinyl alcohol copolymer to silver in silver ammonia solution is (0.2-0.6):

1.

5. The low-ammonia latex medical examination glove according to claim 1, characterized in that, The preparation of the mercaptosilane coupling agent modified porous silica includes: adding tetraethyl orthosilicate to a mixed solution of water and ethanol containing hexadecyltrimethylammonium bromide, then adding hydrochloric acid to control the pH value to 2-4, and carrying out a hydrolysis condensation reaction. After the reaction is completed, calcination is performed to remove hexadecyltrimethylammonium bromide to obtain porous silica; then, the porous silica is modified with a mercaptosilane coupling agent to obtain mercaptosilane coupling agent modified porous silica.

6. The low-ammonia latex medical examination glove according to claim 5, characterized in that, The mercaptosilane coupling agent is γ-mercaptopropyltrimethoxysilane; the amount of mercaptosilane coupling agent added is 8%-18% of the mass of the porous silica.

7. The low-ammonia latex medical examination glove according to claim 5, characterized in that, The volume ratio of water to ethanol is 1:(3-5); the amount of hexadecyltrimethylammonium bromide added is 10%-15% of tetraethyl orthosilicate; The hydrolysis-condensation reaction is carried out at a temperature of 35-60℃.

8. The low-ammonia latex medical examination glove according to claim 1, characterized in that, The reducing agent is glucose, formaldehyde, hydrazine, or tartaric acid; the free radical initiator is azobisisobutyronitrile (AIBN). The concentrated natural latex has a solid content of 60wt%-70wt% and an ammonia content of ≤0.1%.

9. A method for preparing a low-ammonia latex medical examination glove according to any one of claims 1-8, characterized in that, include: Add 5-15 parts of high thermal conductivity silica, 1-2.5 parts of vulcanizing agent, 0.5-1.5 parts of zinc oxide, 0.5-1.5 parts of accelerator, 1-2 parts of antioxidant and 0.1-0.5 parts of surfactant to 100 parts of concentrated natural latex, mix evenly, pour into a mold, dry and vulcanize to obtain low ammonia latex medical examination gloves.

10. The method for preparing low-ammonia latex medical examination gloves according to claim 9, characterized in that, The vulcanization temperature is 90–110°C, and the time is 15–30 min.

Images