CN113150405B - Low-hardness high-tear-resistance natural latex material suitable for space environment and preparation method thereof - Google Patents

Low-hardness high-tear-resistance natural latex material suitable for space environment and preparation method thereof Download PDF

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CN113150405B
CN113150405B CN202110172385.XA CN202110172385A CN113150405B CN 113150405 B CN113150405 B CN 113150405B CN 202110172385 A CN202110172385 A CN 202110172385A CN 113150405 B CN113150405 B CN 113150405B
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王凡
陈兵勇
刘军
闵辉海
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Hubei Institute of Aerospace Chemical Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00—Compositions of natural rubber
    • C08L7/02—Latex
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

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Abstract

The invention relates to a low-hardness high-tear-resistance natural latex material suitable for a space environment and a preparation method thereof.

Description

Low-hardness high-tear-resistance natural latex material suitable for space environment and preparation method thereof
Technical Field
The invention belongs to the field of latex materials, and particularly relates to a low-hardness high-tear-resistance natural latex material suitable for a space environment and a preparation method thereof.
Background
When working in space environment, the harsh conditions of high and low temperature, vacuum, cosmic dust collision, radiation and the like in the space environment must be overcome, so that the latex gloves for working in space environment are required to have the characteristics of high strength, high tearing resistance, high and low temperature resistance, irradiation resistance, no toxicity, softness and comfortable wearing, and various activities can be smoothly carried out in space environment.
In recent years, natural latex products are widely applied to industries such as medicine and health and the like due to excellent air tightness and softness comfort, but the application of the natural latex products in advanced technical industries such as aerospace and the like is greatly limited due to poor strength, particularly tearing performance and aging resistance of the low-hardness natural latex products. In the manufacturing method of nano calcium carbonate latex gloves (CN 1241503C) of Yinyingchun and the like, 5-20% of nano calcium carbonate is added into conventional pre-vulcanized latex or blended latex, so that the tearing performance and the air permeability of a glue film can be improved, when the addition of the nano calcium carbonate is 15%, the tearing strength of the glue film can reach 73.4KN/m at most, but after aging, the tearing strength of the glue film is rapidly reduced to 28.8KN/m, and the tearing performance change rate before and after aging is more than 60%. In "a method for manufacturing a soft latex glove" (CN 103549686B), the present inventors proposed that polyurea elastomer is uniformly sprayed after dip molding of latex gloves to reduce the stress at a constant elongation of 300% of the latex and improve the softness of products, but the present invention is based on nitrile latex and does not consider the tearing property, aging property, etc. of products.
At present, no report about the formula components of the natural latex rubber material with low hardness, high strength, high tear resistance and high and low temperature resistance is found.
Disclosure of Invention
The invention aims to overcome the defects and provide a low-hardness high-tear-resistance natural latex material suitable for a space environment, wherein a natural concentrated latex system is adopted as a main material, and a latex material with low hardness (Shore A hardness is 35 +/-3A), high strength (tensile strength is more than or equal to 30 MPa), high tear resistance (tear strength is more than or equal to 50 kN/m) and high and low temperature resistance is prepared by designing formula raw materials and adjusting the proportion of the raw materials.
In order to achieve the above purpose, the invention provides the following technical scheme:
a low-hardness high-tear-resistance natural latex material suitable for a space environment comprises the following raw materials in parts by weight:
Figure BDA0002939178930000021
Figure BDA0002939178930000031
the accelerator is a dispersion of a mixture of zinc diethyldithiocarbamate and zinc ethylphenyldithiocarbamate;
the anti-aging agent is a dispersion of a mixture of N, N' -di (beta-naphthyl) p-phenylenediamine and 2, 6-di-tert-butyl-4-methylphenol.
Further, the natural latex is ammonia storage concentrated natural latex; the ammonia preservation concentrated natural latex has the total solid content of 60-70 wt%, the dry latex content of 55-65 wt% and the ammonia content of 0.65-0.75 wt%.
Further, the vulcanizing agent is a sulfur dispersion; the sulfur dispersion comprises 45-55% by mass of sulfur and 45-55% by mass of soft water.
Further, the active agent is zinc oxide dispersoid in percentage by mass; the zinc oxide dispersion comprises 50-55% by mass of zinc oxide and 45-50% by mass of soft water.
Further, the anti-aging agent comprises 50-55 wt% of a mixture of N' -di (beta-naphthyl) p-phenylenediamine and 2, 6-di-tert-butyl-4-methylphenol and 45-50 wt% of soft water; the mass ratio of the N, N' -di (beta-naphthyl) p-phenylenediamine to the 6-di-tert-butyl-4-methylphenol is 1: 1-1.2.
Further, the accelerator comprises a mixture of zinc diethyldithiocarbamate and zinc ethylphenyldithiocarbamate, wherein the mass percentage of the mixture is 40-50%, and soft water, the mass percentage of the mixture is 50-60%; the mass ratio of the zinc diethyl dithiocarbamate to the zinc ethyl phenyl dithiocarbamate is 3: 2-2.5.
Further, the diffusant is a soft water solution of 30-35% by mass of sodium methylene dinaphthalene sulfonate.
Further, the thickening agent is casein soft water solution with the mass percentage of 8% -12%.
Further, the stabilizer is an ammonia water solution with the mass percentage concentration of 25% -30%; the solvent in the ammonia water solution is soft water.
A preparation method of a low-hardness high-tear-resistance natural latex material suitable for space environment comprises the following steps:
(1) Sequentially adding soft water, a stabilizer, a dispersing agent and a thickening agent into the natural latex, and mixing;
(2) Sequentially adding a vulcanizing agent, a promoter, an anti-aging agent and an active agent into the product obtained in the step (1) and mixing;
(3) Adding soft water, mixing and standing;
(4) And (4) filtering, homogenizing, standing and processing the product obtained in the step (3) to form.
Further, in the step (3), the standing time is 4-6 h; in the step (4), the filtering method adopts double-layer gauze for filtering; the standing time is more than or equal to 24 hours; the processing and forming method comprises dip forming.
Compared with the prior art, the invention has the following beneficial effects:
(1) The main rubber material of the low-hardness high-tear-resistance natural latex material suitable for the space environment adopts natural latex, the anti-aging agent adopts anti-aging agent DNP (N, N' -di (beta-naphthyl) p-phenylenediamine) and anti-aging agent 264 (2, 6-di-tert-butyl-4-methylphenol) which are used together, and the adding proportion of the two anti-aging agents is adjusted through multiple experiments to obtain the optimal proportion, so that the obtained latex material obtains excellent heat, oxygen and ultraviolet aging resistance and high and low temperature resistance, and the film change rate is lower than 10% before and after the high and low temperature tests and the aging tests;
(2) According to the invention, ZDC (zinc diethyldithiocarbamate) and PX (zinc ethylphenyldithiocarbamate) are used as accelerators, and the addition ratio of the two accelerators is adjusted through multiple experiments to obtain the optimal ratio, so that the hardness of the obtained latex material is only 32 +/-5A, the 300% stress at definite elongation is lower than 2MPa, but the tensile strength and the tearing strength of the adhesive film are high, and the comprehensive performance of the adhesive film is good;
(3) The preparation method of the low-hardness high-tear-resistance natural latex material suitable for the space environment, disclosed by the invention, has the advantages of simple equipment and process and wide applicability.
Detailed Description
The features and advantages of the present invention will become more apparent and appreciated from the following detailed description of the invention.
The word "exemplary" is used exclusively herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments.
The invention relates to a low-hardness high-tear-resistance natural latex material suitable for a space environment, which comprises the following raw materials in parts by weight:
Figure BDA0002939178930000051
Figure BDA0002939178930000061
further, the natural latex is ammonia preserved concentrated natural latex; the ammonia preservation concentrated natural latex has the total solid content of 60-70 wt%, dry latex content of 55-65 wt% and ammonia content of 0.65-0.75 wt%.
Further, the vulcanizing agent is sulfur dispersion; the sulfur dispersion comprises 45-55 wt% of sulfur and 45-55 wt% of soft water.
Further, the active agent is zinc oxide dispersoid with the mass percentage; the zinc oxide dispersoid comprises 50-55 percent by mass of zinc oxide and 45-50 percent by mass of soft water.
Further, the antioxidant is a dispersion of N, N' -di (β -naphthyl) p-phenylenediamine (antioxidant DNP) and 2, 6-di-tert-butyl-4-methylphenol (antioxidant 264); the dispersoid comprises 50 to 55 mass percent of N' -di (beta-naphthyl) p-phenylenediamine and 2, 6-di-tert-butyl-4-methylphenol, and 45 to 50 mass percent of soft water; the mass ratio of the N, N' -di (beta-naphthyl) p-phenylenediamine to the 6-di-tert-butyl-4-methylphenol is 1: 1-1.2.
Further, the accelerator is a dispersion of zinc diethyldithiocarbamate (accelerator ZDC) and zinc ethylphenyldithiocarbamate (accelerator PX); the dispersion comprises 40-50% of zinc diethyldithiocarbamate and zinc ethylphenyldithiocarbamate by mass percentage and 50-60% of soft water by mass percentage; the mass ratio of the zinc diethyl dithiocarbamate to the zinc ethyl phenyl dithiocarbamate is 3: 2-2.5.
Further, the diffusant is a soft water solution of 30-35% by mass of sodium methylene dinaphthalene sulfonate (diffusant NF).
Further, the thickening agent is casein soft water solution with the mass percentage of 8% -12%.
Further, the stabilizer is ammonia water solution with the mass percentage concentration of 25% -30%; the solvent in the ammonia water solution is soft water.
A preparation method of a low-hardness high-tear-resistance natural latex material suitable for space environment comprises the following steps:
(1) Sequentially adding soft water, a stabilizer, a dispersing agent and a thickening agent into the natural latex, and mixing; preferably, natural latex is weighed in a latex preparation barrel, one half of soft water, a stabilizer, a dispersant and a thickener are sequentially added, and the mixture is stirred for 3 to 5min;
(2) Sequentially adding a vulcanizing agent, a promoter, an anti-aging agent and an active agent into the product obtained in the step (1), and stirring for 3-5 min for mixing;
(3) Adding soft water, mixing and standing, preferably, adding the rest half of the soft water, and stirring for 3-5 min; standing for 4-6 h;
(4) Filtering, homogenizing and standing the product obtained in the step (3), and then processing and forming; preferably, the latex after standing is filtered into a homogenizer by using double-layer gauze, the chloroform value of the mucilage is tested to be two primary to two secondary, and the mucilage is kept standing for 24 hours for later use;
further, in the step (4), the processing and forming method includes dip forming, the desired elastic product can be processed by dipping the ceramic or aluminum mold dipped with the coagulant in the cement, and the dipping condition is as follows: the sinking speed is 1.5cm/s, the lifting speed is 2cm/s, and the parking time is 195-1200 s (different according to the thickness of the product).
The main material of the invention adopts a natural concentrated latex system, and special coordination is selected to prepare the latex material with low hardness (Shore A hardness is 35 +/-3A), high strength (tensile strength is more than or equal to 30 MPa), high tear resistance (tear strength is more than or equal to 50 kN/m) and high and low temperature resistance. The performance of the rubber material is influenced by the retention temperature and time, and at low temperature, as the thermal motion of rubber molecules is weakened, the molecular chain segment is frozen, the elasticity is gradually lost, and the service performance is lost. Therefore, the high and low temperature resistance of the material is represented by the high and low temperature cycle (-60 to +60 ℃ high and low temperature alternation, 30 cycles) performance and the like; the aging resistance of the material is characterized by the change of mechanical properties after long-term aging at 70 ℃ (96 h).
Example 1
A preparation method of a low-hardness high-tear-resistance natural latex material suitable for space environment comprises the following steps:
(1) Matching: weighing natural latex in a latex preparation barrel, sequentially adding one half of soft water, a stabilizer, a diffusant and casein, and stirring for 3-5 min;
(2) Then adding a vulcanizing agent, an accelerator, an anti-aging agent and an active agent in sequence, and stirring for 3-5 min;
(3) Finally, adding the rest half of soft water, and stirring for 3-5 min; standing for 4-6 h.
(4) And (3) filtering: and filtering the latex after standing into a homogenizer by using double-layer gauze, homogenizing, and standing the obtained latex for 24 hours for later use. The chloroform value of the homogenate is two beginnings to two endings;
dipping the ceramic or aluminum mould dipped with the coagulant in the mucilage to process the elastic product, wherein the dipping conditions are as follows: the sinking speed is 1.5cm/s, the lifting speed is 2cm/s, and the parking time is 195-1200 s (different according to the thickness of the product).
Table 1 shows the raw material recipe of example 1.
TABLE 1
Figure BDA0002939178930000091
Table 2 shows the main properties of the product obtained in example 1.
TABLE 2
Figure BDA0002939178930000092
Figure BDA0002939178930000101
Example 2
A preparation method of a low-hardness high-tear-resistance natural latex material suitable for space environment comprises the following steps:
(1) Matching: weighing natural latex in a latex preparation barrel, sequentially adding one half of soft water, a stabilizer, a diffusant and casein, and stirring for 3-5 min;
(2) Then adding a vulcanizing agent, an accelerator, an anti-aging agent and an active agent in sequence, and stirring for 3-5 min;
(3) Finally, adding the rest half of soft water, and stirring for 3-5 min; standing for 4-6 h.
(4) And (3) filtering: and filtering the standing latex by using double-layer gauze into a homogenizer, homogenizing, and standing the obtained mucilage for 24 hours for later use. The chloroform value of the homogenate mucilage is two initial to two end;
dipping the ceramic or aluminum mould dipped with the coagulant in the mucilage to process the elastic product, wherein the dipping conditions are as follows: the sinking speed is 1.5cm/s, the lifting speed is 2cm/s, and the standing time is 195-1200 s (which is different according to the thickness of the product).
Table 3 is the raw material recipe of example 2.
TABLE 3
Figure BDA0002939178930000111
Figure BDA0002939178930000121
Table 4 shows the main properties of the product obtained in example 2.
TABLE 4
Figure BDA0002939178930000122
Figure BDA0002939178930000131
Example 3
A preparation method of a low-hardness high-tear-resistance natural latex material suitable for space environment comprises the following steps:
(1) Matching: weighing natural latex in a latex mixing barrel, sequentially adding one half of soft water, a stabilizer, a diffusant and casein, and stirring for 3-5 min;
(2) Then adding a vulcanizing agent, a promoter, an anti-aging agent and an active agent in sequence, and stirring for 3-5 min;
(3) Finally, adding the rest half of soft water, and stirring for 3-5 min; standing for 4-6 h.
(4) And (3) filtering: and filtering the latex after standing into a homogenizer by using double-layer gauze, homogenizing, and standing the obtained latex for 24 hours for later use. The chloroform value of the homogenate is two beginnings to two endings;
dipping the ceramic or aluminum mould dipped with the coagulant in the mucilage to process the elastic product, wherein the dipping conditions are as follows: the sinking speed is 1.5cm/s, the lifting speed is 2cm/s, and the standing time is 195-1200 s (which is different according to the thickness of the product).
Table 5 shows the raw material recipe of example 3
TABLE 5
Figure BDA0002939178930000132
Figure BDA0002939178930000141
Table 6 shows the main properties of the product obtained in example 3.
TABLE 6
Figure BDA0002939178930000142
Figure BDA0002939178930000151
The outdoor space suit palm and finger airtight gloves produced by the formula have good performances of high and low temperature resistance, aging resistance, tear resistance and the like, the storage service life is as long as 6 years, the product has low hardness, good flexibility, comfortable wearing, environmental protection, no toxicity and good air tightness, and volatile matters meet the requirement of hygiene under a low-pressure environment.
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made in the technical solution of the present invention and the embodiments thereof without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Those skilled in the art will appreciate that those matters not described in detail in the present specification are not particularly limited to the specific examples described herein.

Claims (9)

1. The low-hardness high-tear-resistance natural latex material suitable for the space environment is characterized by comprising the following raw materials in parts by mass:
Figure FDA0003795971160000011
the accelerator is a dispersion of a mixture of zinc diethyldithiocarbamate and zinc ethylphenyldithiocarbamate;
the anti-aging agent is a dispersion of a mixture of N, N' -di (beta-naphthyl) p-phenylenediamine and 2, 6-di-tert-butyl-4-methylphenol;
the anti-aging agent comprises a mixture of N, N' -di (beta-naphthyl) p-phenylenediamine and 2, 6-di-tert-butyl-4-methylphenol with the mass percentage of 50-55% and soft water with the mass percentage of 45-50%; the mass ratio of the N, N' -di (beta-naphthyl) p-phenylenediamine to the 2, 6-di-tert-butyl-4-methylphenol is 1-1.2;
the accelerator comprises a mixture of zinc diethyldithiocarbamate and zinc ethylphenyldithiocarbamate, wherein the mass percentage of the mixture is 40-50%, and soft water, the mass percentage of the mixture is 50-60%; the mass ratio of the zinc diethyldithiocarbamate to the zinc ethylphenyldithiocarbamate is 3 to 2.5;
the Shore A hardness of the low-hardness high-tear-resistance natural latex material suitable for the space environment is 32 +/-5A, and the tensile strength is more than or equal to 30MPa.
2. The low durometer high tear natural latex material suitable for use in a space environment of claim 1, wherein said natural latex is ammonia conserving concentrated natural latex; the ammonia preservation concentrated natural latex has the total solid content of 60-70 wt%, the dry latex content of 55-65 wt% and the ammonia content of 0.65-0.75 wt%.
3. The low durometer high tear natural latex material suitable for use in a space environment of claim 1, wherein the vulcanizing agent is a sulfur dispersion; the sulfur dispersion comprises 45-55 wt% of sulfur and 45-55 wt% of soft water.
4. The low durometer high tear resistant natural latex material suitable for use in a space environment of claim 1, wherein said active agent is a zinc oxide dispersion; the zinc oxide dispersoid comprises 50-55% of zinc oxide and 45-50% of soft water.
5. The low-hardness high-tear-resistance natural latex material suitable for the space environment as claimed in claim 1, wherein the dispersing agent is a soft water solution of sodium methylene dinaphthalene sulfonate with a mass percentage of 30-35%.
6. The low-hardness high-tear-resistance natural latex material suitable for use in space environment according to claim 1, wherein said thickener is casein soft water solution in an amount of 8-12% by weight.
7. The low-hardness high-tear-resistance natural latex material suitable for the space environment according to claim 1, wherein the stabilizer is an ammonia water solution with a mass percentage concentration of 25% -30%; the solvent in the ammonia water solution is soft water.
8. The method for preparing a low-hardness and high-tear natural latex material suitable for use in a space environment according to any one of claims 1 to 7, comprising the steps of:
(1) Sequentially adding soft water, a stabilizer, a dispersing agent and a thickening agent into the natural latex, and mixing;
(2) Sequentially adding a vulcanizing agent, a promoter, an anti-aging agent and an active agent into the product obtained in the step (1) and mixing;
(3) Adding soft water, mixing and standing;
(4) And (4) filtering, homogenizing, standing and processing and forming the product obtained in the step (3).
9. The method for preparing a natural latex material with low hardness and high tear resistance suitable for space environment as claimed in claim 8, wherein in the step (3), the standing time is 4-6 h; in the step (4), the filtering method is to adopt double-layer gauze for filtering; the standing time is more than or equal to 24 hours; the processing and forming method comprises dip forming.
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