CN113429643B - Multi-material composite rubber product and preparation method thereof - Google Patents
Multi-material composite rubber product and preparation method thereof Download PDFInfo
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- CN113429643B CN113429643B CN202110603260.8A CN202110603260A CN113429643B CN 113429643 B CN113429643 B CN 113429643B CN 202110603260 A CN202110603260 A CN 202110603260A CN 113429643 B CN113429643 B CN 113429643B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/02—Direct processing of dispersions, e.g. latex, to articles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
- B29C41/14—Dipping a core
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/48—Wearing apparel
- B29L2031/4842—Outerwear
- B29L2031/4864—Gloves
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2307/00—Characterised by the use of natural rubber
- C08J2307/02—Latex
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
- C08J2309/02—Copolymers with acrylonitrile
- C08J2309/04—Latex
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2311/00—Characterised by the use of homopolymers or copolymers of chloroprene
- C08J2311/02—Latex
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/06—Sulfur
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/39—Thiocarbamic acids; Derivatives thereof, e.g. dithiocarbamates
Abstract
The invention relates to the field of chemical engineering, in particular to the field of rubber product preparation, and specifically relates to a multi-material composite rubber product and a preparation method thereof. The multi-material composite rubber product is formed by superposing and compounding a natural rubber layer, a special service performance layer, a synthetic natural mixed rubber layer and a synthetic rubber layer. The invention aims to provide good operation flexibility and meet the requirements of special operation environments by simultaneously utilizing the flexibility of the natural rubber and the properties of irradiation resistance, aging resistance, acid and alkali resistance and the like of the synthetic rubber by facing the natural rubber layer to a human body and facing the synthetic rubber layer to the environment. The invention provides a method for improving the compatibility between natural rubber and synthetic rubber by introducing mixed rubber, so that the multi-material composite rubber product is not layered in the preparation and use processes, and has real practicability.
Description
Technical Field
The invention relates to the field of chemical engineering, in particular to the field of rubber product preparation, and specifically relates to a multi-material composite rubber product and a preparation method thereof.
Background
The common base material of the rubber product is natural rubber, and the natural rubber has excellent comprehensive properties such as excellent high elasticity and mechanical properties, good tear resistance, piercing resistance, abrasion resistance and cutting performance, can provide operators with extremely high flexibility and comfort, and has a good use effect in a common operation environment. However, in special operation environments, such as chemical media involving strong acid, strong base, organic solvent and the like, higher operation temperature, X/gamma irradiation environments and the like, natural rubber has the problems of poor thermal oxygen resistance, acid and alkali resistance and the like, short service life and the like, and is not suitable for the special operation environments.
Synthetic rubbers, including Nitrile Butadiene Rubber (NBR), chloroprene Rubber (CR), butyl rubber (IIR), ethylene propylene diene monomer rubber (EPDM), chlorosulfonated polyethylene rubber (CSM), and the like. Compared with natural rubber, the synthetic rubber has more excellent radiation resistance and aging resistance and is more resistant to chemical media such as acid, alkali and the like. Corresponding base materials can be selected according to special requirements, and if the requirement on air tightness is high, butyl rubber with excellent air tightness can be selected; the requirement on oil resistance is high, and nitrile rubber and the like can be selected. But compared with natural rubber, the general synthetic rubber has higher hardness, low elongation at break and poorer flexibility, can greatly reduce the flexibility of rubber products, and influences the use experience of users.
The natural rubber and the synthetic rubber have larger property difference, and if the two rubbers can be compounded, the respective advantages of the two rubbers are fully utilized, and the obtained compounded rubber simultaneously having excellent properties of the two rubbers can overcome the defects; but the direct compounding is easy to generate the phenomenon of layering of different rubbers.
Disclosure of Invention
The invention aims to provide a multi-material composite rubber product aiming at the advantages of good flexibility, high mechanical strength and good irradiation resistance, aging resistance and acid and alkali resistance of synthetic rubber gloves. In the technical scheme, the synthetic natural mixed rubber is used as a capacity increasing layer of the natural rubber and the synthetic rubber, so that the problem that the natural rubber and the synthetic rubber are thermodynamically incompatible and the product is easily layered is solved, and the product has the advantages of the natural rubber and the synthetic rubber and has practicability.
The invention also aims to provide a preparation method of the multi-material composite rubber product.
In order to achieve the above purpose, the specific technical scheme of the invention is as follows:
a multi-material composite rubber product comprises a natural rubber layer, a special service performance layer, a synthetic natural mixed rubber layer and a synthetic rubber layer. Or removing special performance layer, and the composite rubber product comprises natural rubber layer, synthetic natural rubber mixture layer and synthetic rubber layer.
In a preferred embodiment of the present invention, each of the natural rubber layer, the special performance layer, the synthetic natural rubber mixture layer and the synthetic rubber layer has a thickness of 0.01mm to 2mm.
As a better embodiment in the application, the natural rubber layer is formed by mixing and dipping 85wt% -95 wt% of natural rubber latex and 5wt% -15 wt% of batch; the synthetic natural mixed glue layer is formed by mixing and dipping 5 to 95 weight percent of pre-vulcanized natural latex and 5 to 95 weight percent of pre-vulcanized synthetic latex; the synthetic rubber layer is formed by mixing and dipping 85wt% -95 wt% of synthetic latex and 5wt% -15 wt% of batch mixture.
As a better embodiment in the application, the gamma/X ray shielding layer with special service performance is formed by mixing and dipping 40-65 wt% of natural rubber latex, 4-12 wt% of batch and 25-70 wt% of shielding filler, and the sum of the total mass percentage is 100%.
As a preferred embodiment herein, the compounding agents include sulfur, zinc oxide, accelerators, reinforcing agents, thickeners, and stabilizers; the mass percentage of the sulfur, the zinc oxide, the accelerant, the reinforcing agent, the thickening agent and the stabilizing agent in the whole dipping emulsion is respectively 0.4-5%, 0.5-10%, 0.2-20%, 0.05-10% and 0.1-3%.
As a preferred embodiment in the present application, the reinforcing agent includes any one or a mixture of more of carbon black, white carbon black, titanium dioxide, graphene and precipitated calcium carbonate; the thickening agent comprises a mixture of casein, gelatin, sodium polyacrylate and carboxymethyl fiber; the stabilizer comprises any one or more of ammonia, sodium hydroxide and potassium hydroxide. The accelerator is any one or a mixture of zinc dibutyl dithiocarbamate, zinc diethyl dithiocarbamate and dithiotetramethyl thiuram.
As a preferred embodiment herein, the synthetic latex comprises a mixture of any one or more of nitrile latex, neoprene latex, butyl latex, chlorosulfonated polyethylene latex, styrene-butadiene latex, and acrylate latex.
As a preferred embodiment herein, the shielding filler includes one or more of tungsten, cerium, tin, lanthanum, bismuth, barium, erbium, samarium, gadolinium, tantalum, ytterbium, hafnium, and lead, and oxides or other compounds of these metals.
As a preferred embodiment of the present application, the method for preparing a multi-material compounded rubber product comprises the following steps:
(1) Respectively preparing four pre-vulcanized rubber latexes, namely natural rubber layer latex, special performance layer latex, synthetic natural mixed layer latex and synthetic latex; the prevulcanization operation is prior art, the vulcanization system is selected from sulfur vulcanization systems.
(2) Cleaning the mould, immersing the mould into a coagulant, and drying to obtain a first intermediate mould;
(3) Immersing the first intermediate mould into the natural latex for 5 s-5 min, and then shaping and drying to obtain a second intermediate mould;
(4) Immersing the second intermediate mould into the ray shielding glue emulsion for 5 s-5 min, and then shaping and drying to obtain a third intermediate mould;
(5) Immersing the third intermediate mould into the mixed glue for 5 s-5 min, and then shaping and drying to obtain a fourth intermediate mould;
(6) Immersing the fourth intermediate mould into the synthetic latex for 5 s-5 min, and then shaping and drying to obtain a fifth intermediate mould;
(7) And (3) curling, vulcanizing, demolding, cleaning and drying the dipped gloves to obtain the multi-material composite rubber product.
The impregnation may be performed in the order of (1), (2), (6), (5), (4), (3) and (7).
As a preferred embodiment in the present application, in the step (2), the mold is immersed in a coagulant at normal temperature to 50 ℃, and is baked and dried at 70 ℃ to 140 ℃ for 1min to 10min to obtain a first intermediate mold; in the steps (2) - (6), the setting and drying temperature is 60-100 ℃. In the step (7), the vulcanization conditions are as follows: hot air vulcanization is carried out at the temperature of 80-130 ℃ for 10-120 min; then the water bath vulcanization can be carried out for 70-100 ℃ and 10-120 min, and the water bath vulcanization can be carried out or not.
In the steps (3) - (6), the rubber monolayer formed by dipping four pre-vulcanized rubber latexes, namely natural latex, gamma/X-ray shielding latex, synthetic natural mixed rubber and synthetic latex, is dipped for multiple times if necessary, and then is shaped and dried to enable the prepared rubber monolayer to reach the required thickness.
In the step (2), the coagulant is one or more of calcium chloride, calcium nitrate and barium chloride, and water is added to prepare the mixture with the mass concentration of 10-40%.
Compared with the prior art, the positive effects of the invention are as follows:
the invention divides rubber products (such as gloves, head covers and the like) into an operation surface, a mixed glue layer, an inner layer and a wearing surface, wherein the base material of the operation surface adopts synthetic rubber such as butyronitrile/chloroprene rubber, and the mixed glue layer is prepared by mixing natural latex and synthetic latex according to a certain proportion. The inner layer can adopt natural rubber containing corresponding fillers according to special use performance requirements, such as natural rubber containing shielding fillers. The wearing surface is made of natural rubber. Finally, the rubber product with good flexibility, radiation resistance, acid-base resistance and other special properties is prepared. In the multi-material composite rubber product in the technical scheme, the outer surface and the inner surface of the product are divided into an operation surface and a wearing surface, the operation surface faces the environment, such as the environment of wide-energy radiation, acid and alkali, heat, oxygen and the like, and a base material with excellent resistance to special environment, such as synthetic rubber of butyronitrile or chloroprene rubber and the like, needs to be provided; the wearing surface faces to the human body, the wearing comfort level is an important index, and natural rubber can be used; an optional inner layer is required for special use properties, and for example, a radiation-shielding rubber product is required to include a radiation-shielding inner layer. Finally, through the structural design of the multilayer composite rubber product, the aim of simultaneously having good flexibility and resisting a special environment is fulfilled by utilizing respective advantages of natural rubber and synthetic rubber, so that the multilayer composite rubber product has good comfort and longer service life.
And (II) mixing synthetic latex such as butyronitrile or chloroprene rubber with natural latex according to different proportions to prepare synthetic natural mixed rubber, wherein the mixed rubber is used as a compatibilization layer of a synthetic rubber layer and a natural rubber layer, and the limit that the synthetic rubber layer and the natural rubber layer are thermodynamically incompatible and are easy to delaminate is broken through.
And (III) the inner layer is used as a special service performance layer, if the requirement of ray shielding is met, the inner layer can be used as a ray shielding layer, and natural rubber containing shielding filler is used as a base material, so that the advantage of good flexibility of a natural rubber finished product is fully utilized.
Drawings
FIG. 1 is a schematic cross-sectional view of the rubber article without inner layer (special performance layer) in example 1, wherein: 1-human body; 2-wearing surface: a natural rubber layer; 3-synthetic natural mixed glue layer; 4-operation surface: synthetic rubber layers such as nitrile/chloroprene; 5-environment.
FIG. 2 is a schematic cross-sectional view of a rubber article having an inner layer (special performance layer) in example 3
Wherein: 1-human body; 2-wearing surface: a natural rubber layer; 3-inner layer: a special performance layer; 4-synthetic natural mixed glue layer; 5-operation surface: synthetic rubber layers such as nitrile/chloroprene rubber; 6-environment.
Detailed Description
The multi-material composite rubber product is formed by superposing and compounding a natural rubber layer, a special service performance layer (the layers are increased or decreased according to requirements), a synthetic natural mixed rubber layer and a synthetic rubber layer. The natural rubber layer and the synthetic rubber layer are formed by mixing and dipping 85-95% of rubber latex and 5-15% of batch materials in parts by mass, and the total parts by mass is 100%; the special performance layer, such as a ray shielding layer, is formed by mixing and dipping 40-65% of natural latex, 4-12% of batch and 25-70% of shielding filler by mass, wherein the total mass is 100%; the synthetic natural mixed rubber is formed by mixing pre-vulcanized latex (the pre-vulcanized latex is formed by mixing rubber latex and compounding agents and comprises pre-vulcanized natural latex and pre-vulcanized synthetic latex), wherein the mixed rubber layer is formed by mixing and dipping 5-95% of pre-vulcanized natural latex and 5-95% of pre-vulcanized natural latex in parts by mass, and the total part by mass is 100%.
Compounding agent: comprises sulfur, zinc oxide, accelerant, reinforcing agent, thickening agent and stabilizing agent. The sulfur, the zinc oxide, the accelerant, the reinforcing agent, the thickening agent and the stabilizing agent are respectively 0.4 to 5 percent, 0.5 to 10 percent, 0.2 to 20 percent, 0.05 to 10 percent and 0.1 to 3 percent of the whole dipping emulsion by mass.
The reinforcing agent comprises one or more of carbon black, white carbon black, titanium dioxide, graphene and precipitated calcium carbonate.
The thickener comprises one or more of casein, gelatin, sodium polyacrylate, and carboxymethyl cellulose.
The stabilizer comprises one or more of ammonia, sodium hydroxide and potassium hydroxide. The accelerator is any one or a mixture of zinc dibutyl dithiocarbamate, zinc diethyl dithiocarbamate and dithiotetramethyl thiuram.
The rubber latex comprises: natural latex and synthetic latex, wherein the synthetic latex comprises one or more of butyronitrile latex, neoprene latex, butyl latex, chlorosulfonated polyethylene latex, butylbenzene latex and acrylate latex.
The ray shielding filler comprises one or more of elementary substances such as tungsten, cerium, tin, lanthanum, bismuth, barium, erbium, samarium, gadolinium, tantalum, ytterbium, hafnium, lead and the like, and oxides or other compounds thereof.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
All references to% in this application, unless otherwise indicated, are to be understood as referring to the% by mass.
Example 1:
1. latex preparation
100 parts by weight of natural latex, 2 parts by weight of sulfur, 2 parts by weight of zinc oxide, 1.5 parts by weight of zinc diethyldithiocarbamate, 4 parts by weight of white carbon black, 1 part by weight of carboxymethyl cellulose and 0.7 part by weight of ammonia water are uniformly mixed, and the mixture is placed for 36 hours or more to obtain pre-vulcanized natural latex which is prepared for standby after filtration and bubble removal.
100 parts of butyronitrile latex, 0.5 part of sulfur, 4 parts of zinc oxide, 2 parts of zinc diethyldithiocarbamate, 0.5 part of carbon black, 0.4 part of casein and 0.5 part of potassium hydroxide are uniformly mixed, and the mixture is placed for 36 hours or more to obtain pre-vulcanized butyronitrile latex which is filtered and defoamed for later use.
Mixing the prepared prevulcanized butyronitrile latex and prevulcanized natural latex according to the mass ratio of 10/90, 30/70, 50/50, 70/30 and 90/10, uniformly blending, standing for 24 hours or more to obtain the butyronitrile natural mixed latex, and filtering and defoaming for later use.
2. Impregnated multi-material composite rubber product
Cleaning the mold, soaking in 15% calcium chloride coagulant at room temperature, and drying at 80 deg.C for 4min.
Firstly, dipping the pre-vulcanized butyronitrile latex for 20s, and baking the dipped pre-vulcanized butyronitrile latex at 90 ℃ for 3min after being lifted to shape the pre-vulcanized butyronitrile latex; dipping the butyronitrile natural mixed latex for 10s, and baking the dipped butyronitrile natural mixed latex at 90 ℃ for 2min; finally, the natural latex is dipped for 20s and then is baked for 2min at 90 ℃ after being lifted.
Then hot air vulcanization is carried out for 100 ℃/30min, and water bath vulcanization is further carried out for 95 ℃/30min after the mold stripping is finished. Drying for 20min to obtain the finished product of the butyronitrile natural composite rubber product.
Comparison sample: the butyronitrile natural mixed latex is not dipped in the steps, and the rest steps are consistent.
As a result: the comparative sample which is not dipped with the butyronitrile natural mixed latex is layered after water bath vulcanization, the service performance is lost, and the normal system is not layered. In order to characterize the influence of the mixed adhesive on the peel strength of a system, the GB/T2792-2014 test method for the peel strength of the adhesive tape is consulted, the sample preparation size is 60mmx15mm, and the stretching speed is 300mm/min. Results (for peel-off of the hybrid tape layer from the natural layer) of 0.88N/cm for the 10/90 system, 10.38N/cm for the 30/70 system, 3.50N/cm for the 50/50 system, 0.65N/cm for the 70/30 system, and 0.88N/cm for the 90/10 system. The result shows that the content of butyronitrile in the mixed latex is different from that of the butyronitrile in nature, so that the peel strength can be greatly influenced. And in addition, the mixed latex still does not delaminate after being placed in a water bath at the temperature of 95 ℃ for 24 hours in a 30/70 and 50/50 system, so that the compatibility of natural rubber and nitrile rubber is greatly improved, and the multi-material composite rubber product has practicability.
The butyronitrile natural composite rubber product prepared from the 50/50 system butyronitrile natural mixed latex of the embodiment has the thickness of 0.71mm, the tensile strength of 20.4MPa and the elongation at break of 1485 percent.
Example 2
1. Latex preparation
100 parts by weight of natural latex, 2 parts by weight of sulfur, 2 parts by weight of zinc oxide, 1.5 parts by weight of zinc diethyldithiocarbamate, 4 parts by weight of white carbon black, 1 part by weight of carboxymethyl cellulose and 0.7 part by weight of ammonia water are uniformly mixed, and the mixture is placed for 36 hours or more to obtain pre-vulcanized natural latex which is prepared for standby after filtration and bubble removal.
Uniformly mixing 100 parts of neoprene latex, 2 parts of sulfur, 5 parts of zinc oxide, 2 parts of dithiotetramethyl thiuram, 1 part of carbon black, 0.1 part of sodium polyacrylate and 0.15 part of potassium hydroxide, standing for 36 hours or more to obtain pre-vulcanized neoprene latex, and filtering and defoaming the pre-vulcanized neoprene latex for later use.
Mixing the prepared prevulcanized neoprene latex and prevulcanized natural latex according to the mass ratio of 70/30, uniformly blending, standing for 24 hours or more to obtain neoprene natural mixed latex, and filtering and defoaming the neoprene natural mixed latex for later use.
2. Impregnated multi-material composite rubber product
Cleaning the mold, soaking in 20% calcium chloride coagulant at room temperature, and drying at 90 deg.C for 3min.
Firstly, dipping pre-vulcanized neoprene latex for 15s, lifting and then baking for 2min at 90 ℃ to shape the neoprene latex; soaking the neoprene natural mixed latex for 10s, and baking for 2min at 90 ℃ after lifting; finally dipping the natural latex for 20s, and baking the dipped natural latex at 90 ℃ for 4min after being lifted.
And then hot air vulcanization is carried out at 110 ℃/60min, and the finished product of the chloroprene natural composite rubber product is obtained after the mould is removed.
As a result:
the thickness of the neoprene natural rubber composite product prepared by the embodiment is 0.83mm. The peel strength (the peel of the mixed glue layer and the natural layer) is 7.75N/cm, the tensile strength is 13.4MPa, and the elongation at break is 960 percent.
Example 3
1. Latex preparation
100 parts of natural latex, 2 parts of sulfur, 2 parts of zinc oxide, 1.5 parts of zinc diethyldithiocarbamate, 4 parts of white carbon black, 1 part of carboxymethyl cellulose and 0.7 part of ammonia water are uniformly mixed, placed for 36 hours or more to obtain pre-vulcanized natural latex, and subjected to filtration and defoaming treatment for later use.
100 parts of butyronitrile latex, 0.5 part of sulfur, 4 parts of zinc oxide, 2 parts of zinc diethyldithiocarbamate, 0.5 part of carbon black, 0.4 part of casein and 0.5 part of potassium hydroxide are uniformly mixed, and the mixture is placed for 36 hours or more to obtain pre-vulcanized butyronitrile latex which is filtered and defoamed for later use.
Mixing the prepared pre-vulcanized butyronitrile latex and the pre-vulcanized natural latex according to the mass ratio of 50/50, uniformly blending, standing for 24 hours or more to obtain the butyronitrile natural mixed latex, and filtering and defoaming the butyronitrile natural mixed latex for later use.
Slowly adding 140 parts of cerium oxide powder (the average particle size is not more than 10 micrometers, and the cerium oxide powder needs to be ground in an aqueous solution in advance and fully dispersed) into 100 parts of the natural latex subjected to prevulcanization, uniformly stirring, standing for 24 hours or more to obtain the ray-shielding latex, and filtering and defoaming the ray-shielding latex for later use.
2. Impregnated multi-material composite rubber product
Cleaning the mold, soaking in coagulant of calcium chloride 15% and barium chloride 2% at 40 deg.C, and drying at 100 deg.C for 4min.
Firstly dipping pre-vulcanized natural latex for 20s, and baking for 1min at 80 ℃ after lifting to shape the latex; dipping the radiation shielding latex for 20s, and baking the dipped radiation shielding latex at 80 ℃ for 2min after the dipping, wherein the step is carried out twice; dipping the butyronitrile natural mixed latex for 10s, and baking the mixture for 2min at 80 ℃ after lifting; finally dipping the nitrile latex for 10s, and baking the nitrile latex at 80 ℃ for 1min after lifting.
Then hot air vulcanization is carried out at 100 ℃/60min, and water bath vulcanization is further carried out at 95 ℃/20min after the mold stripping is finished. Drying for 20min to obtain the finished product of the butyronitrile natural composite rubber product.
As a result:
the thickness of the butyronitrile natural composite rubber product containing the shielding latex is 1.10mm, wherein the butyronitrile layer is 0.15mm, the mixed rubber layer is 0.15mm, the shielding rubber layer is 0.55mm, and the natural layer is 0.25mm. The shielding efficiency of the film on gamma rays with energy of 59.5keV is 47 percent; the tensile strength was 15.9MPa, and the elongation at break was 1393%.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (9)
1. A multi-material composite rubber product is characterized in that: the composite rubber product comprises a natural rubber layer, a synthetic natural mixed rubber layer and a synthetic rubber layer; wherein the natural rubber layer is a wearing surface layer, the middle layer is a synthetic natural mixed rubber layer, and the operation surface layer is a synthetic rubber layer; the natural rubber layer is formed by mixing and dipping 85-95 wt% of natural rubber latex and 5-15 wt% of batch mixture; the synthetic natural mixed glue layer is formed by mixing and dipping pre-vulcanized natural latex and pre-vulcanized butyronitrile latex, wherein the mass ratio of the pre-vulcanized butyronitrile latex to the pre-vulcanized natural latex is (10); the synthetic rubber layer is formed by mixing and dipping 85wt% -95 wt% of nitrile-butadiene latex and 5wt% -15 wt% of batch materials.
2. A multi-material composite rubber product is characterized in that: the composite rubber product comprises a natural rubber layer, a synthetic natural mixed rubber layer and a synthetic rubber layer; wherein the natural rubber layer is a wearing surface layer, the middle layer is a synthetic natural mixed rubber layer, and the operation surface layer is a synthetic rubber layer; the natural rubber layer is formed by mixing and dipping 85-95 wt% of natural rubber latex and 5-15 wt% of batch mixture; the synthetic natural mixed glue layer is formed by mixing and dipping pre-vulcanized natural latex and pre-vulcanized neoprene latex, and the mass ratio of the pre-vulcanized neoprene latex to the pre-vulcanized natural latex is (10); the synthetic rubber layer is formed by mixing and dipping 85wt% -95 wt% of neoprene latex and 5wt% -15 wt% of batch materials.
3. A multi-material composite rubber article according to claim 1 or 2, wherein: the composite rubber product also comprises a special service performance layer; the special service performance layer is formed by mixing and dipping 40-65 wt% of natural latex, 4-12 wt% of batch and 25-70 wt% of shielding filler, and the sum of the total mass percentage is 100%.
4. The multi-material composite rubber article according to claim 1 or 2, characterized in that: the batch materials include, but are not limited to, sulfur, zinc oxide, accelerators, strengthening agents, thickeners, and stabilizers.
5. The multi-material composite rubber article of claim 3, wherein: the batch materials include, but are not limited to, sulfur, zinc oxide, accelerators, strengthening agents, thickeners, and stabilizers.
6. A multi-material compounded rubber article according to claim 4, wherein: the reinforcing agent comprises any one or a mixture of more of carbon black, white carbon black, titanium dioxide, graphene and precipitated calcium carbonate; the thickening agent comprises one or more of casein, gelatin, sodium polyacrylate and carboxymethyl fiber; the stabilizer comprises any one or a mixture of more of ammonia water, sodium hydroxide and potassium hydroxide; the accelerator is any one or a mixture of zinc dibutyl dithiocarbamate, zinc diethyl dithiocarbamate and dithiotetramethyl thiuram.
7. A multi-material compounded rubber article according to claim 5, wherein: the reinforcing agent comprises any one or a mixture of more of carbon black, white carbon black, titanium dioxide, graphene and precipitated calcium carbonate; the thickening agent comprises one or more of casein, gelatin, sodium polyacrylate and carboxymethyl fiber; the stabilizer comprises any one or a mixture of more of ammonia water, sodium hydroxide and potassium hydroxide; the accelerator is any one or a mixture of zinc dibutyl dithiocarbamate, zinc diethyl dithiocarbamate and dithiotetramethyl thiuram.
8. The multi-material composite rubber article of claim 3, wherein: the shielding filler comprises elementary substances of tungsten, cerium, tin, lanthanum, bismuth, barium, erbium, samarium, gadolinium, tantalum, ytterbium, hafnium and lead and any one or more of oxides of the metals.
9. The method of making a multi-material compounded rubber article according to any one of claims 5, 7 to 8, characterized by comprising the steps of:
(1) Respectively preparing four pre-vulcanized rubber latexes of natural rubber layer latex, special performance layer latex, synthetic natural mixed layer latex and synthetic rubber layer latex;
(2) Cleaning the mould, immersing the mould into a coagulant, and drying to obtain a first intermediate mould; the coagulant is one or a mixture of calcium chloride, calcium nitrate and barium chloride;
(3) Immersing the first intermediate die into the latex of the natural rubber layer for 5s to 5min, and then shaping and drying to obtain a second intermediate die;
(4) Immersing the second intermediate mould into the special service performance layer latex for 5s to 5min, and then shaping and drying to obtain a third intermediate mould;
(5) Immersing the third intermediate mould into the synthetic natural mixed layer latex for 5s to 5min, and then shaping and drying to obtain a fourth intermediate mould;
(6) Immersing the fourth intermediate mould into the synthetic rubber layer latex for 5s to 5min, and then shaping and drying to obtain a fifth intermediate mould;
(7) And (3) curling, vulcanizing, demolding, cleaning and drying the dipped gloves to obtain the multi-material composite rubber product.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9219658D0 (en) * | 1992-09-17 | 1992-10-28 | Fraser Studios Ltd | Rubber gloves |
| WO2001090236A1 (en) * | 2000-05-19 | 2001-11-29 | Allegiance Corporation | Polymer blends and articles produced therewith |
| FR2896667B1 (en) * | 2006-02-02 | 2008-04-11 | Hutchinson Sa | GLOVE HAVING HIGH CHEMICAL RESISTANCE |
| US20080306200A1 (en) * | 2007-06-11 | 2008-12-11 | Seong Fong Chen | Antistatic gloves and process for making same |
| CN103330309A (en) * | 2012-10-23 | 2013-10-02 | 镇江苏惠乳胶制品有限公司 | Multi-layer composite gloves |
| CN103554565B (en) * | 2013-08-20 | 2015-09-16 | 镇江苏惠乳胶制品有限公司 | A kind of natural rubber and the blended medical gloves of paracril and preparation method thereof |
| CN108433217B (en) * | 2018-04-11 | 2020-03-31 | 山东星宇手套有限公司 | Preparation method of butyronitrile wig bubble anti-slip gloves |
| CN210733488U (en) * | 2019-07-23 | 2020-06-12 | 钱远强 | Sandwich rubber product with antimicrobial effect |
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