CN112480501A - Production process for improving cross-linking density of butyronitrile gloves under condition of not increasing energy consumption - Google Patents
Production process for improving cross-linking density of butyronitrile gloves under condition of not increasing energy consumption Download PDFInfo
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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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- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/126—Halogenation
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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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
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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
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The invention relates to a preparation process of disposable butyronitrile gloves for improving the crosslinking density of the butyronitrile gloves under the condition of not increasing energy consumption.
Description
Technical Field
The invention relates to a production process of disposable butyronitrile gloves, in particular to a production process for improving the crosslinking density of the butyronitrile gloves under the condition of not increasing energy consumption, and belongs to the technical field of butyronitrile gloves.
Background
In recent years, with more and more importance to health and hygiene, the demand of disposable gloves is rapidly increased, and especially butyronitrile gloves which are convenient to use and have stronger functionality are provided. In 2020, as COVID-19 is rapidly diffused in the world, the demand of the butyronitrile gloves is suddenly increased, the productivity of the butyronitrile gloves cannot meet the global supply, and the heat tide of building a factory for the butyronitrile gloves to increase the production line is raised in the world. Compared with latex gloves, the butyronitrile gloves do not contain protein which is easy to cause allergic reaction of human bodies in latex, are not easy to cause allergy, and are low in price; compared with PVC gloves, the PVC gloves have good oil resistance, solvent resistance, puncture resistance, tearing resistance, higher tensile strength, excellent wear resistance, wearing comfort and the like. Butyronitrile gloves are widely used in medical treatment, food, chemical industry, steam repair, agriculture and other fields.
At present, most of butyronitrile gloves are made by adopting sulfur as a vulcanizing agent, zinc dibutyl dithiocarbamate (BZ) as an accelerator and zinc oxide as an active agent through processes of prevulcanization, butyronitrile latex dipping, molding, leaching, vulcanization, surface treatment, drying and the like. The quality of the butyronitrile gloves in the market is uneven due to the fact that the demand of the butyronitrile gloves is continuously increased and the butyronitrile glove production line is in full-load production, the problems of the butyronitrile gloves are mainly and intensively reflected on the defects of frosting, insufficient tensile strength, insufficient elongation, short wearing time and the like, most of the defects are caused by low crosslinking density due to insufficient vulcanization degree of the butyronitrile gloves, and the butyronitrile mixture formula and the vulcanization process are main factors influencing the crosslinking density of the butyronitrile gloves. Under the existing production formula of the butyronitrile gloves, in order to improve the production efficiency, the butyronitrile gloves produced by a factory are not completely vulcanized but are subjected to post vulcanization through the storage and transportation time, so the vulcanization degree of the butyronitrile gloves can be influenced by the post vulcanization time. In order to improve the delivery efficiency, the problem can be solved by increasing the on-line vulcanization degree of the butyronitrile gloves, but the increase of the vulcanization temperature can increase the production energy consumption, and the increase of the vulcanization time can cause the reduction of the production capacity, which is finally not paid.
The invention content is as follows:
the invention aims to provide a preparation process of disposable butyronitrile gloves for improving the cross-linking density of the butyronitrile gloves under the condition of not increasing energy consumption, wherein double accelerators are used, the dosage proportion of sulfur, zinc oxide and the accelerators is optimally adjusted, and the materials are dipped and vulcanized and molded under the control of proper vulcanization conditions; the invention utilizes the synergistic effect among the accelerators, greatly improves the efficiency of the accelerator, further improves the vulcanization speed, increases the vulcanization degree, can prepare the butyronitrile gloves with high crosslinking density under the conditions of not increasing the production energy consumption and reducing the production efficiency, and has strong solvent resistance, difficult frosting, comfortable wearing and high tensile breaking strength.
In order to achieve the purpose, the invention adopts the following technical scheme:
a production process for improving the crosslinking density of nitrile gloves without increasing energy consumption comprises the following steps:
1. raw material
The raw materials mainly comprise the following components:
nitrile latex: a series of acrylonitrile-butadiene latex with acrylonitrile mass percentage of 25-35%
A stabilizer: one or more of sodium dodecyl benzene sulfonate, sodium diisooctyl succinate sulfonate, sodium dibutylnaphthalene sulfonate and sodium tetrapropylene benzene sulfonate
Potassium hydroxide: the purity is more than or equal to 90 percent
Titanium dioxide: the purity is more than or equal to 92 percent
Zinc oxide: the purity is more than or equal to 99.5 percent
Sulfur: the purity is more than or equal to 99 percent
Accelerator A: one of zinc di-n-Butyldithiocarbamate (BZ) and zinc diethyldithiocarbamate (EZ)
Accelerator B: one of zinc dimethyldithiocarbamate (PZ) and zinc ethylphenyldithiocarbamate (PX)
Dispersing agent: anionic surfactants
2. The formula of the nitrile-butadiene mixture prepreg comprises the following steps:
1) formula of butyronitrile latex ingredient
100 portions of butyronitrile latex
0.1 to 0.3 portion of stabilizer
1.5-2 parts of potassium hydroxide
100-200 parts of pure water
2) Auxiliary material formula of ball grinding material
0.8 to 1.5 portions of zinc oxide
0.5 to 1.2 portions of sulfur
0.3-0.6 part of accelerator A, 0.3-0.6 part of accelerator B, and the ratio of accelerator B to accelerator A is 0.8-1.2
1.0-2 parts of titanium dioxide
0.2 to 0.5 part of dispersant
10-20 parts of pure water
3. Preparation process of nitrile butadiene mixture prepreg
Nitrile latex, a stabilizer, potassium hydroxide, ball milling material auxiliary materials and pure water are added into a stirring tank according to the amount of the nitrile mixture formula. Adding butyronitrile latex according to the sequence, diluting the butyronitrile latex by pure water according to a certain proportion, and adding a stabilizer which is diluted by 50-100 times; diluting potassium hydroxide to 1-5% with water in another stirring tank, and adding the diluted potassium hydroxide into a stirring kettle; and grinding the ball milling auxiliary materials according to the amount of the butyronitrile mixture formula by using a grinder for 4-8 hours, adding into a stirring kettle, and supplementing the required pure water. And after the butyronitrile mixture is prepared, continuously stirring for 24-48h at the rotating speed of 80-120 r/min for later use.
4. Butyronitrile glove production process
The butyronitrile glove forming process is shown in figure 1
1) Adding the butyronitrile mixture prepared in the stirring tank into a glue tank 1 and a glue tank 2, wherein the mesh number of a filter screen is not less than 400 meshes;
2) carrying out acid washing, primary water washing, alkali washing, secondary water washing, cleaning by using a cleaning agent, tertiary water washing and drying on the hand mold;
3) dipping the hand mold cleaned in the step 2) in a coagulant solution;
4) drying the hand mould dipped with the coagulant solution in the step 3), and then putting the hand mould into the butyronitrile latex mixture prepared in the step 1) for dipping;
5) drying the hand mold dipped in the glue in the step 4), and then putting the hand mold into the butyronitrile latex mixture prepared in the step 1) again for dipping in the glue;
6) leaching the glue film dipped in the step 5) with clear water, curling, and then placing the glue film in a vulcanizing oven for vulcanizing and drying;
7) and (3) cooling the vulcanized and dried adhesive film obtained in the step 6), placing the adhesive film in chlorine water for chlorine washing, neutralizing with alkaline water, washing with clear water, drying in an oven, and demolding to obtain the butyronitrile gloves.
In the step 2), the surface of the hand mold is cleaner through acid washing, primary water washing, alkali washing, secondary water washing, cleaning by a cleaning agent and tertiary water washing, and subsequent operations of dipping a coagulant, gum dipping, demolding and the like are facilitated. Wherein the pH of the acid washing solution used in acid washing is 2-3, and the pH of the alkaline washing solution used in alkaline washing is 10-11. The cleaning agent is a hand mold cleaning agent, mainly removes metal ions such as calcium, zinc and the like remained on the hand mold, the surface of the cleaned hand mold is smooth, and the hand mold is uniformly free of flow marks when being soaked in a coagulant, so that the surface of the prepared butyronitrile gloves is clean, and the glue film is uniform.
In the step 3), the calcium content of the coagulant solution is controlled to be 8-15 percent, and the surface tension is controlled to be 20-40 mN/m.
In the step 4) and the step 5), the solid content of the mixture is controlled to be 10-20%, the dipping time is 12 +/-5 seconds (adjusted according to the final glove film thickness), the oven temperature is 60-110 ℃, and the baking time is 2-5 min.
In the step 6), the temperature of the leaching water is controlled to be 30-70 ℃, the hardness is controlled to be 500-2000 ppm, the vulcanization temperature is 110 +/-10 ℃, and the vulcanization time is controlled to be 20 +/-10 min.
In the step 7), the concentration of chloride ions in the chlorine water is 300 ppm-800 ppm, and the pH value of the neutralized water is controlled to be 12 +/-2.
The film thickness of the butyronitrile gloves prepared by the invention is 0.05-0.12 mm, the tensile strength of the glove film is more than 28MPa, the elongation is more than 620%, and the swelling index is less than 8.
Drawings
FIG. 1 is a flow chart of an embodiment of the dip forming process of disposable nitrile gloves of the present invention.
Detailed Description
The present invention will be described in detail below with reference to the example gloves and the comparative general example nitrile gloves, but the examples should not be construed as limiting the scope of the present invention.
Example 1
A production process for improving the crosslinking density of nitrile gloves without increasing energy consumption comprises the following steps:
(1) adding 100 parts of butyronitrile latex into a stirring tank, adding pure water for diluting by 2 times, and then adding 0.3 part of stabilizer (sodium dodecyl benzene sulfonate) and 1.5 parts of potassium hydroxide (3% aqueous solution) which are diluted by 50 times by the pure water; 1.5 parts of ball grinding material auxiliary material zinc oxide, 1.2 parts of sulfur, 0.5 part of accelerant A zinc di-n-butyl dithiocarbamate (BZ), 0.4 part of accelerant B zinc dimethyl dithiocarbamate (PZ), 1.5 parts of titanium dioxide, 0.4 part of dispersant sodium polycarboxylate anionic surfactant and 20 parts of pure water, grinding for 6 hours, adding into a stirring tank, and continuously stirring for 36 hours at the rotating speed of 100 plus 120r/min for standby application.
(2) The ceramic hand mold is cleaned and then enters a coagulant tank, is dried by an oven and then is sequentially immersed into a rubber tank 1 and a rubber tank 2, is vulcanized by a vulcanizing box with the temperature of 110 ℃ multiplied by 20min after being dried, leached and curled, is cooled and then is subjected to surface treatment by chlorine water, and finally is cleaned and dried to obtain the butyronitrile gloves. The glove film has a thickness of 0.065 mm, a tensile strength of 29.5MPa, an elongation of 635%, a swelling index of 7.5 and a crosslinking density of 2.46 x 10-4mol/cm3。
Example 2
A production process for improving the crosslinking density of nitrile gloves without increasing energy consumption comprises the following steps:
1) adding 100 parts of butyronitrile latex into a stirring tank, adding pure water for diluting by 2 times, and then adding 0.3 part of stabilizer (sodium dodecyl benzene sulfonate) and 1.5 parts of potassium hydroxide (3% aqueous solution) which are diluted by 50 times by the pure water; 1.2 parts of ball grinding material auxiliary material zinc oxide, 1.1 parts of sulfur, 0.4 part of accelerant A zinc di-n-butyl dithiocarbamate (EZ), 0.4 part of accelerant B zinc ethyl phenyl dithiocarbamate (PX), 1.5 parts of titanium dioxide, 0.4 part of dispersant sodium polycarboxylate anionic surfactant and 20 parts of pure water, grinding for 6 hours, adding into a stirring tank, and continuously stirring for 36 hours at the rotating speed of 100 plus 120r/min for later use.
(2) The ceramic hand mold is cleaned and then enters a coagulant tank, is dried by an oven and then is sequentially immersed into a rubber tank 1 and a rubber tank 2, is vulcanized by a vulcanizing box with the temperature of 110 ℃ multiplied by 20min after being dried, leached and curled, is cooled and then is subjected to surface treatment by chlorine water, and finally is cleaned and dried to obtain the butyronitrile gloves. The glove film has a thickness of 0.065 mm, a tensile strength of 28.9MPa, an elongation of 628%, a swelling index of 7.7 and a crosslinking density of 2.44 x 10-4mol/cm3。
Comparative example 1
Only 0.9 part of accelerator A, zinc di-n-Butyldithiocarbamate (BZ), was added, and the remaining components and method were the same as in example 1.
Comparative example 2
Only 0.9 part of accelerator B zinc dimethyldithiocarbamate (PZ) was added, and the remaining components and method were the same as in example 1.
Comparative example 3
1.6 parts of zinc oxide, 1.3 parts of sulfur, 0.4 part of accelerator A zinc di-n-Butyldithiocarbamate (BZ) and 0.5 part of accelerator B zinc dimethyldithiocarbamate (PZ) were added, and the remaining components and method were the same as in example 1.
Comparative example 4
1.6 parts of zinc oxide, 1.3 parts of sulfur, 0.2 part of accelerator A zinc di-n-butyldithiocarbamate (EZ), and 0.7 part of accelerator B zinc ethylphenyldithiocarbamate (PX) were added, and the remaining components and method were the same as in example 1.
TABLE 1 nitrile glove film Performance test
TABLE 2 Total migration of nitrile glove membranes in different solvents
As can be seen from the above table, the disposable butyronitrile gloves prepared by the invention exceed the performance of gloves produced by the traditional process (the tensile strength of the traditional butyronitrile gloves is more than or equal to 20MPa, the elongation is more than or equal to 500 percent, and the swelling index is 9-12), and the migration resistance of the butyronitrile gloves is improved.
The above description is only a preferred embodiment of the present invention, and these embodiments are based on different implementations of the present invention, and the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (8)
1. A method for improving the cross-linking density of butyronitrile gloves under the condition of not increasing energy consumption is characterized in that butyronitrile latex, a stabilizer, potassium hydroxide, sulfur, an accelerator, zinc oxide and titanium dioxide are prepared into prepreg, then the prepreg is filtered and continuously stirred for 24-48h for standby application to prepare the butyronitrile gloves, and the method is characterized in that: the accelerator is formed by mixing and compounding an accelerator B and an accelerator A, wherein the accelerator A is one of zinc di-n-Butyldithiocarbamate (BZ) and zinc diethyldithiocarbamate (EZ), and the accelerator B is one of zinc dimethyldithiocarbamate (PZ) and zinc ethylphenyldithiocarbamate (PX).
2. The method of claim 1, wherein: accelerator B: accelerator a is 0.8-1.2.
3. The method of claim 1 or 2, wherein: the mass ratio of the butyronitrile latex, the stabilizer, the potassium hydroxide, the sulfur, the zinc oxide and the accelerator is as follows: a stabilizer: potassium hydroxide: sulfur: zinc oxide: accelerator (b): titanium dioxide powder is 100: 0.1-0.3: 1.5-2: 0.5-1.2: 0.8-1.5: 0.6-1.2: 1 to 2.
4. The method of claim 1 or 2, wherein: when the prepreg is used for preparing the nitrile gloves, the vulcanization temperature is 110 +/-10 ℃, and the vulcanization time is 20 +/-10 min.
5. The method of claim 1 or 2, wherein: the acrylonitrile mass percentage content in the butyronitrile latex is 25-35%.
6. The method of claim 1 or 2, wherein: the latex stabilizer is one or more of sodium dodecyl benzene sulfonate, sodium diisooctyl succinate sulfonate, sodium dibutyl naphthalene sulfonate and sodium tetrapropylene benzene sulfonate.
7. Nitrile gloves produced by the process according to any one of claims 1 to 6.
8. The glove of claim 7, wherein: the thickness of the glove film is 0.05-0.12 mm, the tensile strength is more than 25MPa, the elongation is more than 600%, and the swelling index is less than 8.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114031827A (en) * | 2021-12-17 | 2022-02-11 | 中红普林医疗用品股份有限公司 | Butyronitrile gloves with good wearability and no allergic component and preparation method thereof |
| CN114854057A (en) * | 2022-04-26 | 2022-08-05 | 濮阳林氏医疗制品有限公司 | Low-temperature vulcanization package group and preparation method and application thereof |
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| CN114031827A (en) * | 2021-12-17 | 2022-02-11 | 中红普林医疗用品股份有限公司 | Butyronitrile gloves with good wearability and no allergic component and preparation method thereof |
| CN114854057A (en) * | 2022-04-26 | 2022-08-05 | 濮阳林氏医疗制品有限公司 | Low-temperature vulcanization package group and preparation method and application thereof |
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