CN118146571A - Insulating latex glove and preparation method thereof - Google Patents
Insulating latex glove and preparation method thereof Download PDFInfo
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- CN118146571A CN118146571A CN202410578977.5A CN202410578977A CN118146571A CN 118146571 A CN118146571 A CN 118146571A CN 202410578977 A CN202410578977 A CN 202410578977A CN 118146571 A CN118146571 A CN 118146571A
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- latex glove
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- 229910052604 silicate mineral Inorganic materials 0.000 claims abstract description 51
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 45
- 239000002245 particle Substances 0.000 claims abstract description 41
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- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 15
- 239000011593 sulfur Substances 0.000 claims abstract description 15
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 3
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- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
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- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical compound CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 description 2
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- KYBYPDUGGWLXNO-GRVYQHKQSA-N ethane-1,2-diamine;(9z,12z)-octadeca-9,12-dienoic acid Chemical compound NCCN.CCCCC\C=C/C\C=C/CCCCCCCC(O)=O.CCCCC\C=C/C\C=C/CCCCCCCC(O)=O KYBYPDUGGWLXNO-GRVYQHKQSA-N 0.000 description 1
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- ORFSSYGWXNGVFB-UHFFFAOYSA-N sodium 4-amino-6-[[4-[4-[(8-amino-1-hydroxy-5,7-disulfonaphthalen-2-yl)diazenyl]-3-methoxyphenyl]-2-methoxyphenyl]diazenyl]-5-hydroxynaphthalene-1,3-disulfonic acid Chemical compound COC1=C(C=CC(=C1)C2=CC(=C(C=C2)N=NC3=C(C4=C(C=C3)C(=CC(=C4N)S(=O)(=O)O)S(=O)(=O)O)O)OC)N=NC5=C(C6=C(C=C5)C(=CC(=C6N)S(=O)(=O)O)S(=O)(=O)O)O.[Na+] ORFSSYGWXNGVFB-UHFFFAOYSA-N 0.000 description 1
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- KMNUDJAXRXUZQS-UHFFFAOYSA-L zinc;n-ethyl-n-phenylcarbamodithioate Chemical compound [Zn+2].CCN(C([S-])=S)C1=CC=CC=C1.CCN(C([S-])=S)C1=CC=CC=C1 KMNUDJAXRXUZQS-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses an insulating latex glove and a preparation method thereof, and belongs to the technical field of latex gloves. The invention discloses an insulating latex glove which comprises the following raw materials in parts by weight: 100 parts of low-protein natural latex, 1-3 parts of sulfur, 0.5-1.5 parts of vulcanization accelerator, 1-2 parts of antioxidant, 0.5-2 parts of zinc carbonate, 0.5-1 part of potassium hydroxide, 5-15 parts of composite insulating filler and 5-10 parts of liquid polyamide resin; the composite insulating filler comprises a first silicate mineral with an average particle size of 300-800 nm and a second silicate mineral with an average particle size of 3-6 mu m. By adopting a low-protein natural latex system and through the synergistic effect of the composite insulating filler and the liquid polyamide resin, the insulating performance of the glove, particularly the insulating performance after stretching treatment, is improved under the condition of thinner glove thickness, and the insulating latex glove has excellent flexibility.
Description
Technical Field
The invention relates to the technical field of latex gloves, in particular to an insulating latex glove and a preparation method thereof.
Background
Natural latex (NRL) has been widely used in the medical and health industries and in daily life because of its good film forming property, high gel strength, excellent product combination property, good antiviral permeability and good compatibility with human body.
At present, insulating gloves for live working are usually selected and used according to the electric performance requirement levels of different working environments, the main materials of the insulating gloves are usually natural rubber or special rubber such as styrene-butadiene rubber, butyl rubber, ethylene propylene rubber, silicon rubber and the like, and most of the preparation processes are compression molding processes or dipping molding processes. Although products with different electrical performance requirements are available in the market according to different use environment requirements, most of the products are mainly used in high-voltage live working environments, and the products are thicker (generally, the thickness is more than 2 mm), higher in hardness, poor in product sensitivity and not suitable for narrow environments in low-voltage live working environments.
According to the insulating glove for low-voltage live working reported in the prior art CN115670056A, an insulating water-resistant layer is coated on the inner surface of the glove, and the insulating effect is improved, but the product is too thick, the flexibility is poor, and the use is insensitive.
Therefore, there is a need to develop an insulating latex glove which is applied to low-voltage live working, has good flexibility and insulating properties, and has a small thickness.
Disclosure of Invention
The invention aims to overcome the defects of insulating property, flexibility and thickness in the prior art, and provides an insulating latex glove and a preparation method thereof.
In order to achieve the above purpose, the invention adopts the following technical scheme:
an insulating latex glove comprises the following raw materials in parts by weight:
100 parts of low-protein natural latex, 1-3 parts of sulfur, 0.5-1.5 parts of vulcanization accelerator, 1-2 parts of antioxidant, 0.5-2 parts of zinc carbonate, 0.5-1 part of potassium hydroxide, 5-15 parts of composite insulating filler and 5-10 parts of liquid polyamide resin;
The composite insulating filler comprises a first silicate mineral with an average particle size of 300-800 nm and a second silicate mineral with an average particle size of 3-6 mu m.
According to the invention, by adopting the compounding of silicate minerals with two different particle sizes as the composite insulating filler, the insulating performance and flexibility of the latex glove are obviously improved by utilizing the nanocrystalline size effect generated by the filler with a specific size, so that the latex glove still has very excellent insulating performance under the condition of extremely low thickness.
The insulating latex glove of the invention is based on low-protein natural latex, which removes most of the protein components in natural latex. The protein is one of the main components in natural latex and has good electric conductivity. By reducing the protein content, the formation of conductive channels can be reduced, thereby improving the insulating properties of the latex.
In the invention, the composite insulating filler comprises a first silicate mineral with relatively smaller particle size and a second silicate mineral with relatively larger particle size, wherein the average particle size of the first silicate mineral is 300-800 nm, and the average particle size of the second silicate mineral is 3-6 mu m. The first silicate mineral and the second silicate mineral may be the same or different in kind.
The research shows that the silicate mineral compounded with specific particle size can form special nanocrystalline size effect in a latex system. The nanoscale silicate mineral has higher specific surface area, promotes the enhancement of surface effect, and has more obvious interaction with the external environment. When added as a filler to a latex matrix, the nano-sized silicate mineral filled in the latex can more effectively block the flow of electrons or current under the action of an electric field, thereby enhancing insulation properties. When the nanoscale silicate mineral exists, a certain amount of micron-sized silicate mineral (second silicate mineral) with specific particle size is compounded, and the specific micron and nanoscale fillers are matched to generate multi-scale interaction, so that the stability of the composite insulating filler in a latex system is improved, and the insulating property is further improved.
The inorganic material has poor compatibility in a latex system, and particularly silicate minerals with very small particle sizes are difficult to disperse well in the latex system and are easy to agglomerate, so that the insulating property is difficult to improve effectively. According to the invention, the liquid polyamide resin and the composite insulating filler can generate a synergistic effect, so that the composite insulating filler is well dispersed, and in addition, the insulating performance and the flexibility of the glove are further improved. The liquid polyamide resin contains a plurality of active groups, such as unsaturated carbon chains, amino groups, carboxyl groups, amide groups and the like, has certain surface activity, has proper fluid property and viscosity, and can promote the effective dispersion of the composite insulating filler under the action of surface activity and adhesion effect, thereby playing the role of maximally improving the insulativity and the flexibility. The polyamide has good electrical insulation property, and is beneficial to improving the insulation property of the insulating latex glove. In addition, the liquid polyamide resin is added into a low-protein natural latex system, and due to the existence of water in the system, water molecules and polyamide molecules can form a certain hydrogen bond effect, so that the flexibility of the liquid polyamide resin is enhanced, and the flexibility of the insulating latex glove under the condition of extremely thin thickness is further improved; more importantly, under the action of the liquid polyamide resin, the composite insulating filler still has good stability after being stretched, so that the insulating latex glove keeps excellent insulating performance after being stretched.
If silicate minerals with single particle size distribution are adopted in the composite insulating material, the insulating effect with thin thickness is difficult to realize; the too large particle size may cause the decrease of the flexibility of the glove and the poor insulation performance; the particle size is too small, the dispersity of the materials is possibly poor, and the comprehensive performance of the insulating latex glove is poor.
Preferably, the mass ratio of the first silicate mineral to the disilicate mineral in the composite insulating filler is (1.5-3) to 1.
More preferably, the mass ratio of the first silicate mineral to the disilicate mineral in the composite insulating filler is (2.0-2.5) to 1
When the composite insulating filler is in the preferred mass ratio range, the silicate mineral with the nano-scale particle size is more in proportion, the synergistic effect of the first silicate mineral and the disilicate mineral in the composite insulating filler is relatively better, the generated size effect is better, and the insulating performance and the flexibility of the insulating latex glove are better.
The first silicate mineral and the disilicate mineral may each be independently selected from conventional silicate minerals, and the kinds of both may be the same or different. Under the condition of different types, the performance of the insulating latex glove can be better due to the interaction of different forms and different chemicals.
Preferably, the first silicate mineral is talc.
Preferably, the second silicate mineral is halloysite.
Talc is a layered silicate mineral, and the layered structure can effectively block movement of electrons. Halloysite, also known as halloysite nanotubes, is a natural clay mineral with a microtube-like structure, and is generally formed by crimping a plurality of lamellar layers, and because of the existence of interlayer water between the structural unit layers, the halloysite is also called halloysite. The tubular structure of halloysite is favorable for improving the stability of the composite insulating filler in a latex system, and talcum powder with different shapes and halloysite form an interconnected network structure through interaction, so that the insulating performance of the glove is further improved, and particularly, the insulating performance of the glove after stretching treatment is improved.
The interlayer gap generated by the lamellar structure in the talcum powder and the hollow space generated by the tubular structure of halloysite can accommodate the insertion of polymer molecules. When talcum powder, halloysite and liquid polyamide resin are mixed, the liquid polyamide resin can be partially inserted into interlayer gaps of the talcum powder and filled into tubular hollow spaces of the halloysite, so that the bonding compactness of the composite material is improved.
Preferably, the average particle size of the talcum powder is 500-700 nm.
When the talc is within the above-mentioned average particle size range, the synergistic effect with the second silicate mineral is relatively excellent, and the improvement of the insulating properties due to the nanocrystalline size effect is also relatively good.
Preferably, the average particle size of the halloysite is 3.5-5 μm.
Preferably, the average length-diameter ratio of the halloysite is 5-12.
More preferably, the average aspect ratio of halloysite is 6-8.
The average length-diameter ratio of halloysite is the ratio of the tube length to the tube outer diameter of halloysite, and can be detected by a dynamic image granularity particle shape analysis system.
When the halloysite has a long length-diameter ratio, the halloysite tends to mean that the halloysite has a long length, and the halloysite is difficult to cooperate with the first silicate mineral with the nano-scale particle size, so that the insulating performance of the insulating latex glove is reduced, and particularly the insulating performance of the glove is reduced after the glove is stretched. When the length-diameter ratio of halloysite is short, the long strip shape is not obvious, and an effective interconnected network structure is difficult to form with flaky talcum powder. As for halloysite, in the above preferred particle size and aspect ratio ranges, the insulating property and flexibility of the insulating latex glove are improved.
Preferably, the amine value of the liquid polyamide resin is 300-420 mgKOH/g.
More preferably, the amine value of the liquid polyamide resin is 320 to 400mgKOH/g.
Preferably, the viscosity of the liquid polyamide resin is 2000-15000 mPa.s at 40 ℃.
More preferably, the viscosity of the liquid polyamide resin is 3000 to 7000 mPas at 40 DEG C
The amine value of the liquid polyamide resin shows the reactivity, and the liquid polyamide resin with the amine value of 300-420 mgKOH/g has proper reactivity and certain vulcanization promotion effect on a latex system; the viscosity (measured at 40 ℃) of the liquid polyamide resin shows the polymerization degree, molecular weight and fluid property of the polyamide, and the liquid polyamide resin is favorable for better interface bonding between the liquid polyamide resin and the composite insulating filler under the proper viscosity range. The improvement of the comprehensive performance of the insulating latex glove is facilitated by controlling the amine value and the viscosity of the liquid polyamide resin.
The amine value of the liquid polyamide resin is not preferably too high, and in the case of too high, it may mean that the water absorption of the polyamide resin is too strong, resulting in a decrease in the insulating property thereof, and thus, a decrease in the insulating property of the insulating latex glove.
The amine number of the liquid polyamide resin can be measured as follows: accurately weighing a proper amount of liquid polyamide resin sample, placing the liquid polyamide resin sample in a 250mL conical flask, adding about 50mL of acetic acid, shaking until the liquid polyamide resin sample is completely dissolved, slightly heating the liquid polyamide resin sample to completely dissolve if the sample is difficult to dissolve, cooling the liquid polyamide resin sample to room temperature, adding 1-2 drops of crystal violet indicator after the sample is completely dissolved, shaking the liquid polyamide resin sample uniformly, and titrating the liquid polyamide resin sample with a perchloric-acetic acid standard solution of c (HClO 4) =0.1 mol/L, wherein the solution is changed from purple to pure blue, and the end point is obtained.
The viscosity of the liquid polyamide resin can be measured as follows: viscosity testing is carried out by adopting a BROOKFIELD DV-S type digital display viscometer; under the condition of 40 ℃ constant temperature water bath, a certain amount of liquid polyamide resin sample is weighed and placed in a small sample adapter 13R (the dosage of the 31# rotor sample is 9.0mL, the dosage of the 34# rotor sample is 9.4 mL), then a sample cup is placed in a heat-preserving jacket, after a proper rotor model and a proper rotating speed are selected, testing is started, and after a stable value is read out, testing is finished.
Alternatively, the vulcanization accelerator and the anti-aging agent can be the vulcanization accelerator and the anti-aging agent commonly used in latex. The vulcanization accelerator comprises at least one of zinc ethylphenyl dithiocarbamate (PX), N-cyclohexyl-2-benzothiazole sulfenamide and tetraethylthiuram disulfide; the anti-aging agent comprises 2, 6-di-tert-butyl-p-cresol.
Preferably, the nitrogen content of the low-protein natural latex is 0.1-0.2 wt.%.
Preferably, the average thickness of the insulating latex glove is less than or equal to 1.0mm.
More preferably, the average thickness of the insulating latex glove is 0.5-0.8 mm.
The average thickness of the insulating latex glove means an average value of the palm center position single layer thickness, the wrist position single layer thickness, and the finger position single layer thickness of the insulating latex glove.
At a thinner thickness, the insulating latex glove is more comfortable to use, but the smaller the thickness, the lower the insulating property and the tensile resistance of the glove are caused.
The invention also provides a preparation method of the insulating latex glove, which comprises the following steps:
s1, mixing a first silicate mineral with a second silicate mineral subjected to heat treatment to obtain a mixed filler;
S2, mixing the mixed filler prepared in the step S1 with part of liquid polyamide resin, and performing ball milling at 60-80 ℃ to obtain premix;
s3, adding the premix prepared in the step S2 into low-protein natural latex, adding the rest liquid polyamide resin, sulfur, a vulcanization accelerator, an anti-aging agent, zinc carbonate and potassium hydroxide, uniformly stirring, and then performing presulfiding to obtain presulfiding latex;
S4, using the pre-vulcanized latex to prepare the insulating latex glove.
In the invention, the second silicate mineral with relatively larger particle size is heated and then mixed with the first silicate mineral, and the insulating property of the material can be improved and the activity of the material can be increased by heating, so that the synergistic effect of the two silicate minerals is better.
Preferably, in step S1, the conditions of the heating treatment are: the temperature is 250-300 ℃ and the time is 5-8 hours.
In the present invention, the conditions of the heat treatment of the second silicate mineral need to be strictly controlled, and particularly the temperature of the heat treatment is not preferably too low or too high. If the temperature of the heating treatment is too low, the time of the heating treatment is too short, or the heating treatment is not performed, so that an effective activation effect is difficult to achieve, and the combination effect of the second silicate mineral and the first silicate mineral is poor; or the second silicate mineral produces an excessively strong reinforcing effect on the material, so that the flexibility of the insulating latex glove is rather lowered. When the temperature is too high, the morphology structure of the silicate mineral may be damaged or the crystal structure may be changed, for example, the tubular structure of halloysite may be damaged, and the polar group of the second silicate mineral may be reduced, the activity may be weakened, and the insulation performance and the flexibility of the insulation latex glove are affected.
Preferably, in step S1, the part of the liquid polyamide resin is 30-50wt.% of the total amount of the liquid polyamide resin.
In the step S2, the mixed filler and the liquid polyamide resin are mixed for ball milling treatment, and the organic liquid polyamide resin and the inorganic composite insulating filler form better combination at the interface through ball milling, so that the interface combination strength of the composite material is improved, the stress concentration is reduced, the overall performance stability of the material is improved, and the tight combination of the liquid polyamide resin and the composite insulating filler is realized. The premix after ball milling treatment is contacted and mixed with low-protein natural latex, so that the composite insulating filler can be well dispersed in a latex system, and the synergistic effect of each component for improving the insulating property and the flexibility is exerted.
Preferably, in step S2, the ball milling process conditions are as follows: the rotating speed is 60-80 rpm, and the time is 60-90 min.
In the ball milling process of the liquid polyamide resin/composite insulating filler ball milling system, a certain mechanochemical effect can be generated at a proper rotating speed (60-80 rpm) in the ball milling treatment process, and the interface bonding effect among the components is enhanced. However, if the rotation speed is too high, structural change of the composite insulating filler may be caused, especially when halloysite is adopted as the second silicate mineral, the second silicate mineral has a certain length-diameter ratio and is in a strip shape with a tubular structure, and the change of the length-diameter ratio and the damage of the tubular structure are particularly affected by the rotation speed of ball milling, so that improvement of insulation and softness of the hand is further affected; at too low a rotational speed, the mechanochemical effect brought by ball milling is insufficient, and the improvement is not obvious.
In the step S3, after the components are uniformly stirred, the solid content of the system can be regulated to be 30-50% by deionized water, and then the pre-vulcanized latex is obtained.
For step S4, the following may be specifically included:
Cleaning and drying the glove mould, then, putting the glove mould into the coagulating liquid, and taking out and drying;
Immersing the glove mould into the pre-vulcanized latex, and taking out and drying after the immersion is finished;
Then curling the glove, dipping a release agent, demoulding and draining to obtain a primary blank of the latex glove;
and vulcanizing the initial blank of the latex glove at 120 ℃ for 20-40 min to obtain the insulating latex glove.
Compared with the prior art, the invention has the beneficial effects that:
The invention discloses an insulating latex glove and a preparation method thereof, wherein a low-protein natural latex system is adopted, and the insulating performance of the glove, particularly the insulating performance after stretching treatment, is improved under the severe condition of a thinner glove thickness by the synergistic effect of a composite insulating filler and liquid polyamide resin, and the insulating latex glove has excellent flexibility and is particularly suitable for low-voltage live working.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples, which are not intended to limit the present invention in any way. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art. Unless otherwise specified, the reagents and materials used in the present invention are all commercially available and are specifically described as follows:
Low protein natural latex, purchased from new material technology, 61% solids, 0.1% nitrogen;
The vulcanization accelerator is PX, and is sold in the market;
the anti-aging agent is 2, 6-di-tert-butyl-p-cresol, which is commercially available;
Silicate mineral powder:
talc powder-1 with average particle diameter of 350nm,
Talc powder-2 with average particle diameter of 520nm,
Talcum powder-3 with an average particle size of 670nm,
Talcum powder-4 with average grain size of 800nm,
Talcum powder-5 with average particle size of 1500nm,
Talcum powder-1 to 5 is obtained by grinding, screening and selecting R7 talcum powder products of Yiruishi company;
talc-6, having an average particle size of 2 μm, available from R7 of Yiruishi Co,
Talcum powder-7 with average particle size of 4.1 μm, obtained from Fuquan FQ-88A product of Yingdong, haifeng,
Talcum powder-8 with an average particle size of 13 μm and purchased from sea city chemical engineering TY90-13-A;
kaolin, having an average particle size of 5 μm, available from Rhawn, R005369;
Halloysite-1, average particle size of 3.7 μm, average aspect ratio of 5.3,
Halloysite-2, average particle size of 4.2 μm, average aspect ratio of 7.5,
Halloysite-3, average particle size of 4.6 μm, average aspect ratio of 11.6,
Halloysite-4, average particle size of 5.5 μm, average aspect ratio of 25.1,
Halloysite-1 to 4, purchased from Guangzhou Runwo materials technology, is further screened and selected from different production processes and batches of products to obtain halloysite products with different average particle sizes and average length-diameter ratios; wherein the average length-diameter ratio of halloysite is obtained by analyzing and detecting the particle size and the particle shape of the dynamic images of the Baite BT-2900;
Liquid polyamide resin:
liquid polyamide resin-1, with an amine number of 350 mgKOH/g and a viscosity of 5500 mPa s at 40 ℃, purchased from Shanghai complex new material technology YD-8140;
liquid polyamide resin-2, with an amine number of 340 mgKOH/g, a viscosity of 10000 mPa s at 40 ℃, purchased from Shanghai complex new material technology YD-8125;
Liquid polyamide resin-3, having an amine number of 370 mgKOH/g, a viscosity of 2200 mPa s at 40 ℃, available from Versamid 140;
Liquid polyamide resin-4, amine number 420 mgKOH/g, viscosity 5000 mPa s at 40 ℃, available from microphone Lin Juxian amine curative 651;
liquid polyamide resin-5, having an amine number of 310 mgKOH/g and a viscosity at 40℃of 6000 mPa s, obtainable from VERSAMIND polyamide curing agent type 300.
Example 1
The embodiment provides an insulating latex glove, which is prepared by the following method:
S1, weighing the following components in parts by weight: 100 parts of low-protein natural latex, 1.5 parts of sulfur, 1 part of vulcanization accelerator, 1 part of antioxidant, 0.75 part of zinc carbonate, 0.75 part of potassium hydroxide, 8 parts of liquid polyamide resin (adopting liquid polyamide resin-1), and 10 parts of composite insulating filler (consisting of 6.7 parts by weight of talcum powder (adopting talcum powder-2) and 3.3 parts by weight of halloysite (adopting halloysite-2);
Heating halloysite at 300 ℃ for 5.5 hours, cooling to room temperature, and mixing with talcum powder to obtain a mixed filler;
S2, mixing the mixed filler prepared in the step S1 with 40wt.% of liquid polyamide resin, and performing ball milling at 80rpm for 60min at 65 ℃ to obtain premix;
S3, adding the premix prepared in the step S2 into low-protein natural latex, adding the rest 60wt.% of liquid polyamide resin, sulfur, a vulcanization accelerator, an anti-aging agent, zinc carbonate and potassium hydroxide, uniformly stirring, adding deionized water to adjust the solid content of a system to 46%, placing in a water bath environment at 60 ℃, heating under the condition of slow stirring at 90rpm, periodically detecting the vulcanization degree, taking out the latex when the vulcanization degree reaches three ends, standing for 5h for sedimentation, filtering, and completing presulfiding to obtain presulfiding latex;
S4, cleaning and drying the glove mould, immersing the glove mould in a coagulating agent, and taking out and drying;
Immersing the glove mould into the pre-vulcanized latex for 15-20 s, taking out and drying;
Dipping again into the pre-vulcanized latex for 12-15 s, taking out and drying;
Then curling the glove, dipping a release agent, demoulding and draining to obtain a primary blank of the latex glove;
And vulcanizing the initial blank of the latex glove, wherein the vulcanizing condition is 120 ℃ for 20-40 min, so that the insulating latex glove is obtained, and the average thickness of the insulating latex glove is controlled to be 0.60+/-0.01 mm by adjusting the dipping time.
Examples 2 to 4
Examples 2-4 provide an insulating latex glove, the preparation method is similar to example 1, the difference is that: the talc used in examples 2 to 4 was talc-1, talc-3 and talc-4, respectively.
Examples 5 to 7
Examples 5-7 provide an insulating latex glove, the preparation method is similar to example 1, the difference is that: halloysite used in examples 5 to 7 was halloysite-1, halloysite-3, and halloysite-4, respectively.
Examples 8 to 10
Examples 8-10 provide an insulating latex glove, the preparation method is similar to example 1, the difference is that:
10 parts of the composite insulating filler of example 8 consists of 7 parts by weight of talc-2 and 3 parts by weight of halloysite-2;
10 parts of the composite insulating filler of example 9 consists of 6 parts by weight of talc-2 and 4 parts by weight of halloysite-2;
10 parts of the composite insulating filler of example 10 consists of 7.5 parts by weight of talc-2 and 2.5 parts by weight of halloysite-2.
Examples 11 to 14
Examples 11-14 provide an insulating latex glove, the preparation method is similar to example 1, the difference is that: the liquid polyamide resins used in examples 11 to 14 were respectively liquid polyamide resin-2 to liquid polyamide resin-5.
Example 15
Example 15 provides an insulating latex glove, similar to example 1, with the difference that: in the step S1, 10 parts of composite insulating filler consists of 6.7 parts by weight of talcum powder-2 and 3.3 parts by weight of talcum powder-7; and (3) carrying out heating treatment on the talcum powder-7 at 300 ℃ for 5.5 hours, cooling to room temperature, and then mixing with the talcum powder-2 to obtain the mixed filler.
Example 16
Example 16 provides an insulating latex glove, similar to example 1, with the difference that: in the step S1, 10 parts of composite insulating filler consists of 6.7 parts by weight of talcum powder-2 and 3.3 parts by weight of kaolin; the kaolin is heated for 5.5 hours at 300 ℃, cooled to room temperature and then mixed with talcum powder-2 to obtain the mixed filler.
Example 17
Example 17 provides an insulating latex glove, similar to example 1, with the difference that: in the step S1, halloysite-1 is subjected to heat treatment at 250 ℃ for 8 hours; in step S2, ball milling treatment was performed at 60rpm for 90 minutes.
Example 18
Example 18 provides an insulating latex glove, prepared similarly to example 1, with the difference that: in step S1, halloysite-1 is heat treated at 550℃for 6 hours.
Example 19
Example 19 provides an insulating latex glove, similar to example 1, with the difference that: in step S2, ball milling treatment was performed at 300rpm for 30min.
Example 20
Example 20 provides an insulating latex glove, similar to example 1, with the difference that: in the step S1, the following components are weighed according to the parts by weight: 100 parts of low-protein natural latex, 2.5 parts of sulfur, 1.5 parts of vulcanization accelerator, 1.5 parts of antioxidant, 1.5 parts of zinc carbonate, 1 part of potassium hydroxide, 5 parts of liquid polyamide resin (adopting liquid polyamide resin-1), and 15 parts of composite insulating filler (consisting of 10 parts by weight of talcum powder (adopting talcum powder-2) and 5 parts by weight of halloysite (adopting halloysite-2)).
Comparative example 1
Comparative example 1 provides an insulating latex glove, prepared similarly to example 1, with the difference that:
In the step S1, the following components are weighed according to the parts by weight: 100 parts of low-protein natural latex, 1.5 parts of sulfur, 1 part of vulcanization accelerator, 1 part of antioxidant, 0.75 part of zinc carbonate, 0.75 part of potassium hydroxide and 10 parts of composite insulating filler (consisting of 6.7 parts by weight of talcum powder (talcum powder-2) and 3.3 parts by weight of halloysite (halloysite-2);
i.e. free of liquid polyamide resin;
In the step S2, ball milling is carried out on the mixed filler prepared in the step S1 at the temperature of 60-80 ℃ at 80rpm for 60min, and premix is obtained.
Comparative example 2
Comparative example 2 provides an insulating latex glove, prepared similarly to example 1, with the difference that:
In the step S1, the following components are weighed according to the parts by weight: 100 parts of low-protein natural latex, 1.5 parts of sulfur, 1 part of vulcanization accelerator, 1 part of antioxidant, 0.75 part of zinc carbonate, 0.75 part of potassium hydroxide and 18 parts of composite insulating filler (consisting of 12 parts by weight of talcum powder (talcum powder-2) and 6 parts by weight of halloysite (halloysite-2);
Namely, the composite insulating filler does not contain liquid polyamide resin, and the content of the composite insulating filler is correspondingly increased;
In the step S2, ball milling is carried out on the mixed filler prepared in the step S1 at the temperature of 60-80 ℃ at 80rpm for 60min, and premix is obtained.
Comparative example 3
Comparative example 3 provides an insulating latex glove, prepared similarly to example 1, with the difference that:
Weighing the following components in parts by weight: 100 parts of low-protein natural latex, 1.5 parts of sulfur, 1 part of vulcanization accelerator, 1 part of antioxidant, 0.75 part of zinc carbonate, 0.75 part of potassium hydroxide and 8 parts of liquid polyamide resin (liquid polyamide resin-1); i.e. without composite insulating filler;
after the components were directly and uniformly mixed, deionized water was added to adjust the solid content of the system to 46%, and precuring was performed in accordance with the conditions of example 1 to prepare an insulating latex glove.
Comparative example 4
Comparative example 4 provides an insulating latex glove, prepared similarly to example 1, with the difference that:
Weighing the following components in parts by weight: 100 parts of low-protein natural latex, 1.5 parts of sulfur, 1 part of vulcanization accelerator, 1 part of antioxidant, 0.75 part of zinc carbonate, 0.75 part of potassium hydroxide and 18 parts of liquid polyamide resin (liquid polyamide resin-1);
Namely, the composite insulating filler is not contained, and the content of the liquid polyamide resin is correspondingly increased;
after the components were directly mixed, deionized water was added to adjust the solid content of the system to 46%, and precuring was performed in accordance with the conditions of example 1 to prepare an insulating latex glove.
Comparative example 5
Comparative example 5 provides an insulating latex glove, prepared similarly to example 1, with the difference that: 10 parts of composite insulating filler consists of 10 parts of talcum powder-6;
and (3) carrying out heating treatment on talcum powder-6 at 300 ℃ for 5.5 hours, and cooling to room temperature to obtain the mixed filler.
Comparative example 6
Comparative example 6 provides an insulating latex glove, prepared similarly to example 1, with the difference that: 10 parts of composite insulating filler consists of 10 parts of talcum powder-2;
and (3) carrying out heating treatment on talcum powder-2 at 300 ℃ for 5.5 hours, and cooling to room temperature to obtain the mixed filler.
Comparative example 7
Comparative example 7 provides an insulating latex glove, prepared similarly to example 1, with the difference that: 10 parts of composite insulating filler consists of 10 parts by weight of halloysite-2;
heating halloysite-2 at 300 ℃ for 5.5 hours, and cooling to room temperature to obtain the mixed filler.
Comparative example 8
Comparative example 8 provides an insulating latex glove, prepared similarly to example 1, with the difference that: 10 parts of composite insulating filler consists of 6.7 parts by weight of talcum powder-2 and 3.3 parts by weight of talcum powder-8; and (3) carrying out heating treatment on talcum powder-8 at 300 ℃ for 5.5 hours, cooling to room temperature, and then mixing with talcum powder-2 to obtain the mixed filler.
Comparative example 9
Comparative example 9 an insulating latex glove was prepared in a similar manner to example 1, with the difference that: in the step S1, halloysite-2 is directly mixed with talcum powder-2 to obtain a mixed filler, namely, the halloysite is not subjected to heating treatment.
Comparative example 10
Comparative example 10 an insulating latex glove was prepared in a similar manner to example 1, with the exception that:
S1, preparing a mixed filler in the same way as in the example 1;
S2, adding the mixed filler prepared in the step S1 into low-protein natural latex, adding all the liquid polyamide resin, sulfur, a vulcanization accelerator, an anti-aging agent, zinc carbonate and potassium hydroxide, uniformly stirring, adding deionized water to adjust the solid content of a system to 46%, placing in a water bath environment at 60 ℃, heating under the condition of slow stirring at the rotating speed of 90rpm, periodically detecting the vulcanization degree, taking out the latex when the vulcanization degree reaches three ends, standing for 5h for sedimentation, filtering, and completing presulfiding to obtain presulfiding latex;
s3, cleaning and drying the glove mould, immersing the glove mould in a coagulator, and taking out and drying the glove mould;
Immersing the glove mould into the pre-vulcanized latex for 15-20 s, taking out and drying;
Dipping again into the pre-vulcanized latex for 12-15 s, taking out and drying;
Then curling the glove, dipping a release agent, demoulding and draining to obtain a primary blank of the latex glove;
And vulcanizing the initial blank of the latex glove, wherein the vulcanizing condition is 120 ℃ for 20-40 min, so that the insulating latex glove is obtained, and the average thickness of the insulating latex glove is controlled to be 0.60+/-0.01 mm by adjusting the dipping time.
Comparative example 11
Comparative example 11 an insulating latex glove was prepared in a similar manner to example 1, with the difference that: in the step S1, the following components are weighed according to the parts by weight: 100 parts of low-protein natural latex, 2.5 parts of sulfur, 1.5 parts of vulcanization accelerator, 1.5 parts of antioxidant, 1.5 parts of zinc carbonate, 1 part of potassium hydroxide, 5 parts of liquid polyamide resin (adopting liquid polyamide resin-1), and 20 parts of composite insulating filler (consisting of 13.3 parts by weight of talcum powder (adopting talcum powder-2) and 6.7 parts by weight of halloysite (adopting halloysite-2)).
Comparative example 12
Comparative example 12 an insulating latex glove was prepared in a similar manner to example 1, with the exception that: in the step S1, the following components are weighed according to the parts by weight: 100 parts of low-protein natural latex, 2.5 parts of sulfur, 1.5 parts of vulcanization accelerator, 1.5 parts of antioxidant, 1.5 parts of zinc carbonate, 1 part of potassium hydroxide, 15 parts of liquid polyamide resin (adopting liquid polyamide resin-1), and 15 parts of composite insulating filler (consisting of 10 parts by weight of talcum powder (adopting talcum powder-2) and 5 parts by weight of halloysite (adopting halloysite-2)).
Performance testing
The following performance tests were performed on the insulating latex gloves prepared in each of the examples and comparative examples, and it should be noted that 30 glove parallel tests were performed for each performance test item, and an average value was taken:
(1) Initial insulation properties:
The test environment temperature is 23+/-5 ℃ and the relative humidity is 45-50%, and an alternating current verification voltage test is adopted: the alternating voltage is gradually boosted from a lower value at a constant speed of about 1000V/s, the first pressurization to 5kV, the duration of 3min, the value of the leakage current recorded; if the leakage current is not more than 10mA, reducing the voltage at the same speed, then carrying out second pressurization, reducing the voltage after the second pressurization to 10kV, and observing whether the glove breaks down in the second pressurization process; if the leakage current exceeds 10mA, the second pressurization is not performed and is indicated as "-" in Table 1.
(2) Insulation properties after stretching:
Cutting a dumbbell-shaped test block from the palm part of the insulating latex glove according to the method of GB T17622-2008, pulling the test block to a state of 300% of tensile elongation at a rate of 2 mm/min, keeping for 10 minutes, and then recovering to relax; and then carrying out an alternating current verification voltage test: the ac voltage was gradually increased from a lower value to 5kV at a constant speed of about 1000V/s for 3min, and the value of the leakage current was recorded.
(3) Flexibility:
The test environment temperature is 23+/-5 ℃ and the relative humidity is 45-50%, dumbbell-shaped test blocks are cut from the palm part of the insulated latex glove according to the method of GB T17622-2008, a tensile test is carried out at the speed of 500 mm/min by using a tensile tester, and the tensile stress when the tensile elongation is 300% and 500% is recorded according to the tensile stress-tensile elongation curve and is respectively recorded as F 300、F500.
The test results are shown in Table 1.
Table 1 test results
From the above results, it can be seen that:
The insulating latex glove prepared by the embodiment of the invention has good insulating performance (the leakage current in the initial insulating performance is less than or equal to 8.6mA and the minimum leakage current can reach 3.1 mA) at a thinner thickness (about 0.60 mm), and has excellent breakdown resistance; the insulation performance is still better after the stretching treatment (the leakage current after stretching is less than or equal to 9.3 mA); the insulating glove also has excellent flexibility, and the higher the flexibility is, the larger the corresponding tensile stress is, and the higher the tensile stress (F 300≥7.0MPa,F500 is more than or equal to 26.4 MPa) is at 300% and 500% of tensile elongation.
According to comparative examples 1 to 4 and example 1, it can be seen that the composite insulating filler and the liquid polyamide resin in the insulating latex glove of the present invention have a synergistic effect on the flexibility of the insulating property of the glove.
According to comparative examples 5-8, it can be seen that particle size control of the composite insulating filler plays a key role in flexibility of insulating performance of the insulating latex glove.
As can be seen from comparative example 9, when the silicate filler is not heat-treated, the bonding effect of the two silicate fillers is poor and the insulating performance of the insulating latex glove is poor. As can be seen from comparative example 10, when the pre-mixed ball milling treatment of the liquid polyamide resin and the composite insulating filler is not performed, the binding force between the organic and inorganic components is poor, particularly resulting in very poor insulating properties of the glove after stretching.
According to comparative example 11, the excessive content of the composite insulating filler not only makes the initial insulating property of the glove poor, but also causes serious deterioration of the insulating property of the glove after stretching. According to comparative example 12, when the content of the liquid polyamide resin is too large, the mechanical properties thereof may be affected due to the excessive influence of water in the latex system during the processing, and the overall properties of the latex glove may be poor.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (12)
1. The insulating latex glove is characterized by comprising the following raw materials in parts by weight:
100 parts of low-protein natural latex, 1-3 parts of sulfur, 0.5-1.5 parts of vulcanization accelerator, 1-2 parts of antioxidant, 0.5-2 parts of zinc carbonate, 0.5-1 part of potassium hydroxide, 5-15 parts of composite insulating filler and 5-10 parts of liquid polyamide resin;
The composite insulating filler comprises a first silicate mineral with an average particle size of 300-800 nm and a second silicate mineral with an average particle size of 3-6 mu m.
2. The insulating latex glove according to claim 1, wherein the mass ratio of the first silicate mineral to the disilicate mineral in the composite insulating filler is 1.5-3:1.
3. The insulating latex glove according to claim 1, wherein the first silicate mineral is talc and the second silicate mineral is halloysite.
4. The insulating latex glove according to claim 3, wherein the talc has an average particle diameter of 500 to 700nm.
5. The insulating latex glove according to claim 3, wherein the halloysite has an average particle diameter of 3.5 to 5 μm and an average aspect ratio of 5 to 12.
6. The insulating latex glove according to claim 1, wherein the liquid polyamide resin has an amine value of 300 to 420mgkoh/g.
7. The insulating latex glove according to claim 6, wherein the viscosity of the liquid polyamide resin is 2000 to 15000 mPa-s at 40 ℃.
8. The insulating latex glove according to claim 1, wherein the low-protein natural latex has a nitrogen content of 0.1 to 0.2wt.%.
9. The method for preparing the insulating latex glove according to any one of claims 1 to 8, which is characterized by comprising the following steps:
s1, mixing a first silicate mineral with a second silicate mineral subjected to heat treatment to obtain a mixed filler;
S2, mixing the mixed filler prepared in the step S1 with part of liquid polyamide resin, and performing ball milling at 60-80 ℃ to obtain premix;
s3, adding the premix prepared in the step S2 into low-protein natural latex, adding the rest liquid polyamide resin, sulfur, a vulcanization accelerator, an anti-aging agent, zinc carbonate and potassium hydroxide, uniformly stirring, and then performing presulfiding to obtain presulfiding latex;
S4, using the pre-vulcanized latex to prepare the insulating latex glove.
10. The method of manufacturing an insulating latex glove according to claim 9, wherein in step S2, the part of the liquid polyamide resin is 30 to 50wt.% of the total amount of the liquid polyamide resin.
11. The method for producing an insulating latex glove according to claim 9, wherein in step S1, the conditions of the heat treatment are: the temperature is 250-300 ℃ and the time is 5-8 hours.
12. The method for preparing an insulating latex glove according to claim 9, wherein in step S2, the ball milling process conditions are as follows: the rotating speed is 60-80 rpm, and the time is 60-90 min.
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