CN115093511B - Butyronitrile butadiene styrene composite latex for dipped gloves and preparation method and application thereof - Google Patents
Butyronitrile butadiene styrene composite latex for dipped gloves and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08J2351/04—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to rubbers
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Abstract
The invention provides butyronitrile butadiene styrene composite latex for gum dipping gloves as well as a preparation method and application thereof, and relates to the technical field of synthetic latex materials for manufacturing liner butyronitrile gloves. The preparation method comprises the following steps: heating the initial reaction material to 35-45 ℃ and reacting for 0.5-0.8h; heating to 55-65 ℃, adding a butylbenzene oil phase material, a first emulsifying agent material and a first initiator material, and reacting for 0.2-0.5h; cooling to 35-45 ℃, adding the butyronitrile oil phase material, the second emulsifying agent material and the second initiator material, and reacting for 0.5-0.8h; controlling the adding rate of the butylbenzene oil phase material and the butyronitrile oil phase material, and repeatedly heating and cooling until the composite latex with the solid content of 38-40% and the composite structure of the multilayer butyronitrile and the multilayer butylbenzene is synthesized. The composite latex has the advantages of styrene butadiene rubber and nitrile butadiene rubber, and has excellent oil resistance, weather resistance, wear resistance and acid and alkali resistance.
Description
Technical Field
The invention relates to the technical field of synthetic latex materials for manufacturing liner butyronitrile gloves, in particular to butyronitrile butadiene styrene composite latex for gum dipping gloves and a preparation method and application thereof.
Background
The gum dipping gloves are seen everywhere in various industries as labor protection articles, and with the implementation of national labor protection article policies, the demand of the labor protection articles is increased, and the requirements on the labor protection articles are higher and higher. Because of the different environmental and applicable requirements of various industries, the performance of glove blanks and latex needs to be further improved.
Common impregnated labor protection gloves in the market have defects in the aspects of wear resistance, seepage prevention, acid and alkali resistance, high temperature resistance and the like. The pure butyronitrile impregnated gloves have defects in brightness and wear resistance; the pure styrene butadiene glove has poor oil resistance.
Chinese patent CN111875739A discloses a preparation technology of carboxylic styrene-butadiene latex, the carboxylic styrene-butadiene latex prepared by the scheme has the advantages of less harmful odor, low cost, simple process, environment-friendly materials, good acid and alkali resistance, capability of resisting corrosion of various strong acids, strong bases and general chemicals, acid and alkali resistance superior to that of common butyronitrile gloves, excellent heat and cold resistance, capability of adapting to operation in various severe environments, capability of providing a new material for the labor protection industry, and limited application range of the gloves, wherein the butadiene-styrene latex has poor oil resistance and is a novel material; the Chinese patent CN1166706C discloses a preparation method of carboxyl butyronitrile latex for thick dipped product lining gloves, the butyronitrile latex prepared by the scheme has better viscosity and higher film forming property than normal latex, meets the production and use requirements of oil-resistant lining gloves, and simultaneously gives consideration to the production of dipped gloves, but the gloves have certain defects in brightness and wear resistance and have poor cold resistance.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide butyronitrile butadiene styrene composite latex for a gum dipping glove and a preparation method and application thereof, which solve the problems of insufficient brightness and wear resistance and poor cold resistance of the existing butyronitrile latex prepared dipping glove; the butyronitrile butadiene styrene composite latex for the gum dipping gloves with excellent oil resistance, weather resistance, wear resistance and acid and alkali resistance can be obtained, and the application range of the gloves is favorably expanded.
The invention is realized by the following steps:
in a first aspect, the invention provides a preparation method of butyronitrile butylbenzene composite latex for gum dipping gloves, which comprises the following steps:
(1) Uniformly mixing deionized water, electrolyte, a pH buffering agent, an emulsifier component, a molecular weight regulator, acrylonitrile, unsaturated carboxylic acid and unsaturated carboxylic ester, adding butadiene and an initiator component to form an initial reaction material, heating to 35-45 ℃, and reacting for 0.5-0.8h; the mass ratio of deionized water, electrolyte, pH buffer, emulsifier component, unsaturated carboxylic acid, unsaturated carboxylic ester, molecular weight regulator, acrylonitrile, butadiene and initiator component in the initial reaction material is 300-340:0.03-0.06:0.03-0.06:0.3-0.7:0.5-0.9:0-0.3:0.05-0.09:2.5-5:7-10:0.03-0.04;
(2) Heating to 55-65 ℃, adding a butylbenzene oil phase material, a first emulsifying agent material and a first initiator material, and reacting for 0.2-0.5h to form a butylbenzene layer; the butylbenzene oil phase material comprises the following raw materials in a mass ratio of 30-45:0.2-0.4:2-4:0-1.5:8 to 11 of styrene, a molecular weight regulator, an unsaturated carboxylic acid ester and butadiene;
(3) Cooling to 35-45 ℃, adding the butyronitrile oil phase material, the second emulsifying agent material and the second initiator material, and reacting for 0.5-0.8h to form a butyronitrile layer; the butyronitrile oil phase material comprises the following raw materials in a mass ratio of 30-50:0.5-1.5:6-10:0-3:80 to 100 parts of acrylonitrile, a molecular weight regulator, unsaturated carboxylic acid ester and butadiene;
(4) Repeating the step (2) and the step (3) until composite latex with the solid content of 38-40% is synthesized, wherein the composite latex has a composite structure of multilayer butyronitrile and multilayer butylbenzene;
wherein the adding rate of the butylbenzene oil phase material is 160-200kg/h, and the adding rate of the butyronitrile oil phase material is 150-180kg/h;
the raw materials of the first emulsifying agent material and the second emulsifying agent material both comprise, by mass, 50-70:0.3-0.5:0.3-0.5:4-7 deionized water, electrolyte, pH buffer and emulsifier components;
the raw materials of the first initiator charge and the second initiator charge respectively comprise, by mass, 15-25:0.3-0.5 deionized water and an initiator component.
In an alternative embodiment, the first emulsifier material and the second emulsifier material are each added at a rate of 55 to 66kg/h; the addition rates of the first initiator charge and the second initiator charge are both 17-20kg/h.
In an optional embodiment, the styrene-butadiene oil phase material, the nitrile-butadiene oil phase material, the first emulsifier material, the second emulsifier material, the first initiator material and the second initiator material are all uniformly added by using a syringe pump.
In an optional embodiment, the temperature rising rate for rising to 55-65 ℃ is 2-3 ℃/min, and the temperature falling rate for falling to 35-45 ℃ is 3-4 ℃/min.
In alternative embodiments, the electrolyte is one or a mixture of potassium chloride and potassium pyrophosphate;
preferably, the pH buffer is one or a mixture of sodium bicarbonate, potassium carbonate or potassium hydrogen phosphate;
preferably, the unsaturated carboxylic acid is one or a mixture of methacrylic acid and acrylic acid;
preferably, the unsaturated carboxylic ester is one or a mixture of ethyl acrylate, butyl acrylate and ethyl methacrylate;
preferably, the emulsifier component is one or a mixture of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, potassium oleate and sodium naphthalene sulfonate;
preferably, the molecular weight regulator is one or a mixture of tert-dodecyl mercaptan and diisopropyl xanthogen disulfide;
preferably, the initiator component is one or a mixture of two of potassium persulfate and ammonium persulfate.
In an alternative embodiment, the preparation method of the butyronitrile butadiene styrene composite latex for the gum dipping glove further comprises the following steps of degassing and post-treating the composite latex: and adjusting the pH value of the composite latex to 6-8, adding a terminator and a defoaming agent, diluting, vacuum degassing to obtain the required solid content, and adding an antioxidant and a bactericide to obtain the finished product.
In a second aspect, the invention provides a butyronitrile butadiene styrene composite latex for a gum dipping glove, which is prepared by the preparation method of the butyronitrile butadiene styrene composite latex for the gum dipping glove according to any one of the foregoing embodiments.
In a third aspect, the present invention provides a dipped glove, which comprises a glove blank, wherein the glove blank is dipped with the butyronitrile butadiene styrene composite latex for dipped gloves according to the previous embodiments.
In a fourth aspect, the invention provides a method for preparing a dipped glove, wherein a glove blank is preheated to 45-55 ℃, dipped with a coagulant for 1-3 seconds and then dipped into the butyronitrile butadiene styrene-butadiene composite latex for the dipped glove according to the previous embodiment for 2-6 seconds, and then the dipped glove is placed into an oven for drying at 70-90 ℃ for 20-40 min and then heated to 110-130 ℃ for drying for 1-2h.
The invention has the following beneficial effects:
the butyronitrile butadiene styrene composite latex for the dipping gloves improves the problems of certain defects in brightness and wear resistance and poor cold resistance of the dipping gloves prepared by the existing butyronitrile latex; the styrene-butadiene latex has poor oil resistance and the use range of the glove is limited; according to the butyronitrile butadiene styrene composite latex for the gum dipping glove, a specific stepped temperature rising and cooling operation is performed, and when the temperature rises and falls to a reaction temperature each time, a butadiene styrene oil phase material and a butyronitrile oil phase material are respectively added, and an emulsifier and an initiator are simultaneously added for a mixed reaction, so that a multilayer butyronitrile and butadiene styrene composite structure is generated; the whole operation process is controllable, and the excellent performance of each layer of rubber material is ensured; the continuous feeding of the injection pump is adopted, so that the core-shell structure of the colloidal particles can be alternately changed, the fusion of two rubber materials in the using process is facilitated, and the stability of a latex system is improved; the composite latex has the advantages of styrene butadiene rubber and nitrile butadiene rubber, has excellent oil resistance, weather resistance, wear resistance and acid and alkali resistance, saves the production cost of gloves, has excellent use value, and plays a positive role in providing a new material for the labor protection industry.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The invention provides a preparation method of butyronitrile butadiene styrene composite latex for a gum dipping glove, which comprises the following steps:
s1, preparing materials.
The butylbenzene oil phase material, the first emulsifying agent material, the first initiator material, the butyronitrile oil phase material, the second emulsifying agent material and the second initiator material are fully and uniformly mixed for later use before being added.
Specifically, preparing a butylbenzene oil phase material: adding styrene, molecular weight regulator, unsaturated carboxylic acid and unsaturated carboxylic ester in sequence according to the following mass ratio, charging nitrogen, vacuumizing, repeatedly replacing for three times, adding butadiene, stirring for 20-25min, and storing at 25 ℃ for later use. The butylbenzene oil phase material comprises the following raw materials in a mass ratio of 30-45:0.2-0.4:2-4:0-1.5:8-11 of styrene, a molecular weight regulator, unsaturated carboxylic acid, unsaturated carboxylic ester and butadiene.
Preparing a butyronitrile oil phase material: adding acrylonitrile, molecular weight regulator, unsaturated carboxylic acid and unsaturated carboxylic ester in sequence according to the following mass ratio, charging nitrogen, vacuumizing, repeatedly replacing for three times, adding butadiene, stirring for 20-25min, and storing at 25 ℃ for later use. The butyronitrile oil phase material comprises the following raw materials in a mass ratio of 30-50:0.5-1.5:6-10:0-3:80-100 parts of acrylonitrile, a molecular weight regulator, unsaturated carboxylic acid, unsaturated carboxylic ester and butadiene.
Preparing a first emulsifying agent material and a second emulsifying agent material: sequentially adding deionized water, electrolyte, pH buffer and emulsifier according to the following mass ratio, charging nitrogen, vacuumizing, repeatedly replacing for three times, stirring for 20-25min, and storing at 25 ℃ for later use. The raw materials of the first emulsifying agent material and the second emulsifying agent material both comprise the following components in a mass ratio of 50-70:0.3-0.5:0.3-0.5:4-7 deionized water, an electrolyte, a pH buffer, and an emulsifier component.
Formulation of the first initiator charge and the second initiator charge: adding initiator components and deionized water according to the following mass ratio, stirring for 20-25min, and storing at 25 ℃ for later use. The raw materials of the first initiator charge and the second initiator charge respectively comprise the following components in a mass ratio of 15-25:0.3-0.5 deionized water and an initiator component.
S2, synthesizing composite latex.
(1) Uniformly mixing deionized water, electrolyte, pH buffer, emulsifier component, molecular weight regulator, acrylonitrile, unsaturated carboxylic acid and unsaturated carboxylic ester, adding butadiene and initiator component to form initial reaction material, heating to 35-45 deg.C, and reacting for 0.5-0.8h.
The mass ratio of deionized water, electrolyte, pH buffer, emulsifier component, unsaturated carboxylic acid, unsaturated carboxylic ester, molecular weight regulator, acrylonitrile, butadiene and initiator component in the initial reaction material is 300-340:0.03-0.06:0.03-0.06:0.3-0.7:0.5-0.9:0-0.3:0.05-0.09:2.5-5:7-10:0.03-0.04.
(2) Heating to 55-65 ℃, adding the butylbenzene oil phase material, the first emulsifying agent material and the first initiator material, and reacting for 0.2-0.5h to form a butylbenzene layer.
Specifically, heating to 55-65 ℃ at a heating rate of 2-3 ℃/min, and then adding a butylbenzene oil phase material, a first emulsifying agent material and a first initiator material by using a syringe pump, wherein the adding rate of the butylbenzene oil phase material is 160-200kg/h, and the adding rate of the first emulsifying agent material is 55-66kg/h; the adding speed of the first initiator charge is 17-20kg/h; reacting for 0.2-0.5h to form a butylbenzene layer.
(3) Cooling to 35-45 ℃, adding the butyronitrile oil phase material, the second emulsifying agent material and the second initiator material, and reacting for 0.5-0.8h to form a butyronitrile layer;
specifically, the temperature is reduced to 35-45 ℃ at the cooling rate of 3-4 ℃/min, then a butyronitrile oil phase material, a second emulsifying agent material and a second initiator material are added by adopting an injection pump, and the adding rate of the butyronitrile oil phase material is 150-180kg/h; the adding speed of the second emulsifying agent is 55-66kg/h; the adding speed of the second initiator is 17-20kg/h; reacting for 0.5-0.8h to form a butyronitrile layer.
(4) And (3) repeating the step (2) and the step (3) until composite latex with the solid content of 38-40% is synthesized, wherein the composite latex has a composite structure of multilayer butyronitrile and multilayer butylbenzene.
The selection of the electrolyte, the pH buffer, the unsaturated carboxylic acid ester, the emulsifier component, the molecular weight regulator and the initiator component in the steps (1), (2) and (3) is as follows:
electrolytes include, but are not limited toMixing with one or two of potassium chloride and potassium pyrophosphate; the pH buffer comprises one or a mixture of more of sodium bicarbonate, potassium carbonate and potassium hydrogen phosphate; the unsaturated carboxylic acid is one or a mixture of methacrylic acid and acrylic acid; the unsaturated carboxylic acid ester comprises but is not limited to one or a mixture of ethyl acrylate, butyl acrylate and ethyl methacrylate; the emulsifier component comprises but is not limited to one or a mixture of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, potassium oleate and sodium naphthalene sulfonate; molecular weight regulators include, but are not limited to, one or a mixture of two of tertiary dodecyl mercaptan and diisopropyl xanthogen disulfide; wherein the structural formula of the diisopropyl xanthogen disulfide is as follows:
. The initiator component includes, but is not limited to, one or a mixture of two of potassium persulfate and ammonium persulfate. It should be noted that the selection of the emulsifier components used in the first emulsifier and the second emulsifier is also selected with reference to the above description, and correspondingly, the selection of the initiator components used in the first initiator and the second initiator is also selected with reference to the above description.
And S3, latex degassing and post-treatment.
Adjusting the pH value of the composite latex to 6-8, adding a terminator and a defoaming agent, diluting, vacuum degassing to obtain the required solid content, and adding an antioxidant and a bactericide to obtain the finished product.
Specific selection of the terminator, the defoamer, the antioxidant and the bactericide is referred to the prior art, and is not limited in the application, and the application only lists the terminator, the defoamer, the antioxidant and the bactericide used in the actual production process, but is not considered to limit the selection of the terminator, the defoamer, the antioxidant and the bactericide. For example, the terminating agent may be sodium ferulate; the defoaming agent can be water-based defoaming agent, and the antioxidant can be phenolic antioxidant; the bactericide may be a quaternary ammonium salt bactericide.
According to the method, through specific stepped heating and cooling operations, when the temperature is raised and cooled to the reaction temperature each time, a butylbenzene oil phase material and a butyronitrile oil phase material are respectively added, and an emulsifier and an initiator are simultaneously added for a mixing reaction, so that a multilayer butyronitrile and butylbenzene composite structure is generated; the whole operation process is controllable, and the excellent performance of each layer of rubber material is ensured; the continuous feeding of the injection pump is adopted, so that the core-shell structure of the colloidal particles can be alternately changed, the fusion of two rubber materials in the using process is facilitated, and the stability of a latex system is improved; the prepared butyronitrile butadiene styrene composite latex for the gum dipping glove has the advantages of butadiene styrene rubber and butyronitrile rubber, has excellent oil resistance, weather resistance, wear resistance and acid and alkali resistance, saves the production cost of the glove, has excellent use value, and plays a positive role in providing new materials for the labor protection industry.
The butyronitrile butadiene styrene composite latex for the gum dipping gloves can be widely applied to preparation of the gum dipping gloves.
Specifically, the application also provides a dipped glove which comprises a glove blank, wherein the glove blank is dipped with the butyronitrile butadiene styrene composite latex for the dipped glove. The specific preparation method comprises the following steps: preheating the glove blank to 45-55 ℃, then dipping the glove blank with a coagulant for 1-3 seconds, then dipping the glove blank into the butyronitrile butylbenzene composite latex for the gum dipping glove in the embodiment for 2-6 seconds, drying the glove blank in a 70-90 ℃ oven for 20-40 min, and then heating to 110-130 ℃ and drying for 1-2h. The prepared dipped gloves have excellent performance and excellent wear resistance and oil resistance.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment provides butyronitrile butadiene styrene composite latex for a gum dipping glove, and the preparation method comprises the following steps:
the ingredients were dosed according to the formulations in the dosing tank as shown in table 1.
TABLE 1 raw material formulation for each material in example 1
| Materials (kg) | First/second emulsifier bucket | Butyronitrile oil phase charging bucket | Butylbenzene oil phase material tank | First/second initiator tank | Initial reaction kettle charging bucket |
| Deionized water | 60 | - | - | 20 | 320 |
| Potassium pyrophosphate | 0.4 | - | - | - | 0.04 |
| Potassium hydrogen phosphate | 0.4 | - | - | - | 0.04 |
| Sodium dodecyl benzene sulfonate | 6 | - | - | - | 0.5 |
| Methacrylic acid | - | 8 | 3 | - | 0.7 |
| Acrylic acid butyl ester | - | 1 | 0.5 | - | 0.1 |
| Tertiary dodecyl mercaptan | - | 1 | 0.3 | - | 0.07 |
| Acrylonitrile | - | 40 | - | - | 3.5 |
| Styrene (meth) acrylic acid ester | - | - | 35 | - | - |
| Butadiene | - | 90 | 9 | - | 8 |
| Potassium persulfate | - | - | - | 0.4 | 0.035 |
S1, preparing materials.
Preparing a butylbenzene oil phase material: styrene, tert-dodecyl mercaptan, methacrylic acid and butyl acrylate are added in sequence according to the weight parts in the table 1, nitrogen is filled, vacuum pumping is carried out, replacement is carried out repeatedly for three times, butadiene is added, stirring is carried out for 25min, and the mixture is stored for standby at 25 ℃.
Preparing a butyronitrile oil phase material: adding acrylonitrile, tert-dodecyl mercaptan, butyl acrylate and methacrylic acid in the weight portions shown in Table 1, filling nitrogen, vacuumizing, replacing repeatedly for three times, adding butadiene, stirring for 25min, and storing at 25 ℃ for later use.
Preparing a first emulsifying agent material and a second emulsifying agent material: deionized water, potassium pyrophosphate, potassium hydrogen phosphate and sodium dodecyl benzene sulfonate are added in sequence according to the weight parts in the table 1, nitrogen is filled, vacuum pumping is carried out, replacement is carried out repeatedly for three times, stirring is carried out for 25min, and the mixture is stored for standby at 25 ℃.
Formulation of the first initiator charge and the second initiator charge: adding potassium persulfate and deionized water according to the weight parts in the table 1, stirring for 25min, and storing at 25 ℃ for later use.
S2, synthesizing composite latex.
(1) Deionized water, potassium pyrophosphate, potassium hydrogen phosphate and sodium dodecyl benzene sulfonate are sequentially added according to the weight parts in the table 1, stirred for 25min, then tert-dodecyl mercaptan, acrylonitrile, methacrylic acid and butyl acrylate are sequentially added, stirring is started, nitrogen is filled, vacuum pumping is carried out, replacement is carried out for three times repeatedly, butadiene and an initiator are added, the temperature is raised to 40 ℃, and the reaction is carried out for 0.75h.
(2) Heating to 60 ℃, controlling the speed of a styrene butadiene oil phase material injection pump to be 180kg/h, controlling the speed of a first emulsifier material injection pump to be 60kg/h, controlling the speed of a first initiator material injection pump to be 18kg/h, and reacting for 0.25h.
(3) And (3) cooling to 40 ℃, continuously adding the mixture by using an injection pump, wherein the speed of the injection pump for the butyronitrile oil phase material is 160kg/h, the speed of the injection pump for the second emulsifying agent material is 60kg/h, the speed of the injection pump for the second initiating agent material is 18kg/h, and reacting for 0.75h.
(4) And (4) repeating the step (2) and the step (3) to carry out alternate heating and cooling steps until the composite latex with the solid content of 38-40% is synthesized.
And S3, latex degassing and post-treatment.
Adjusting the pH value of the composite latex to about 7, adding a terminating agent (sodium dimethyl dithiocarbamate), adding a water-based defoaming agent, diluting, performing vacuum degassing until the required solid content is more than 43%, and adding a certain amount of phenol antioxidant and quaternary ammonium salt bactericide to obtain a finished product.
Example 2
Example 2 is substantially the same as example 1 except that the reaction raw materials are formulated differently, and the formulation of this example is shown in table 2.
TABLE 2 raw material formulation of each material in example 2
| Material (kg) | First/second emulsifierCharging bucket | Butyronitrile oil phase charging bucket | Butylbenzene oil phase material tank | First/second initiator tank | Initial reaction kettle charging bucket |
| Deionized water | 70 | - | - | 25 | 340 |
| Potassium pyrophosphate | 0.5 | - | - | - | 0.06 |
| Potassium hydrogen phosphate | 0.5 | - | - | - | 0.06 |
| Sodium dodecyl benzene sulfonate | 7 | - | - | - | 0.7 |
| Methacrylic acid | - | 10 | 4 | - | 0.9 |
| Acrylic acid butyl ester | - | 3 | 1.5 | - | 0.3 |
| Tertiary dodecyl mercaptan | - | 1.5 | 0.4 | - | 0.09 |
| Acrylonitrile | - | 50 | - | - | 5 |
| Styrene (meth) acrylic acid ester | - | - | 45 | - | - |
| Butadiene | - | 100 | 11 | - | 10 |
| Potassium persulfate | - | - | - | 0.5 | 0.04 |
Example 3
Example 3 is substantially the same as example 1 except that the reaction raw materials are formulated differently, and the formulation of this example is shown in table 3.
TABLE 3 raw material recipe for each material in example 3
| Material (kg) | First/second emulsifier bucket | Butyronitrile oil phase charging bucket | Butylbenzene oil phase material tank | First/second initiator tank | Initial reaction kettle charging bucket |
| Deionized water | 50 | - | - | 15 | 300 |
| Potassium pyrophosphate | 0.3 | - | - | - | 0.03 |
| Potassium hydrogen phosphate | 0.3 | - | - | - | 0.03 |
| Sodium dodecyl benzene sulfonate | 4 | - | - | - | 0.3 |
| Methacrylic acid | - | 6 | 2 | - | 0.5 |
| Acrylic acid butyl ester | - | 0 | 0 | - | 0 |
| Tertiary dodecyl mercaptan | - | 0.5 | 0.2 | - | 0.05 |
| Acrylonitrile | - | 30 | - | - | 2.5 |
| Styrene (meth) acrylic acid ester | - | - | 30 | - | - |
| Butadiene | - | 80 | 8 | - | 7 |
| Potassium persulfate | - | - | - | 0.3 | 0.03 |
Example 4
Compared with the example 1 with unchanged polymerization formula, the composite latex synthesis steps are changed as follows: the temperature is increased to 35 ℃ and the reaction is carried out for 0.8h. Heating to 55 ℃, wherein the injection pump speed of the styrene-butadiene oil phase material is 160kg/h, the injection pump speed of the first emulsifying agent material is 55kg/h, the injection pump speed of the first initiating agent material is 17kg/h, and reacting for 0.5h. And (3) cooling to 35 ℃, continuously adding the mixture by using an injection pump, wherein the speed of the injection pump for the butyronitrile oil phase material is 150kg/h, the speed of the injection pump for the second emulsifying agent material is 55kg/h, the speed of the injection pump for the second initiating agent material is 17kg/h, and reacting for 0.8h. The temperature was raised and lowered repeatedly until a latex with a solids content of 38% was synthesized.
Example 5
Compared with the example 1 with unchanged polymerization formula, the composite latex synthesis steps are changed as follows: the temperature is increased to 45 ℃ and the reaction is carried out for 0.5h. Heating to 65 ℃, wherein the injection pump speed of the styrene-butadiene oil phase material is 200kg/h, the injection pump speed of the first emulsifying agent material is 66kg/h, the injection pump speed of the first initiating agent material is 20kg/h, and reacting for 0.2h. And (3) cooling to 45 ℃, continuously adding the mixture by using an injection pump, wherein the speed of the injection pump for the butyronitrile oil phase material is 180kg/h, the speed of the injection pump for the second emulsifying agent material is 66kg/h, the speed of the injection pump for the second initiating agent material is 20kg/h, and reacting for 0.5h. The temperature was raised and lowered repeatedly until a latex with a solids content of 38% was synthesized.
Comparative example 1
Step one, 380kg of deionized water, 0.44kg of potassium pyrophosphate, 0.44kg of potassium hydrogen phosphate and 5.5kg of sodium dodecyl benzene sulfonate are sequentially added according to the weight parts, stirring is carried out for 25min, then 1.37kg of tert-dodecyl mercaptan, 56.1kg of acrylonitrile, 8.7kg of methacrylic acid and 2.2kg of butyl acrylate are sequentially added, stirring is started, nitrogen filling and vacuum pumping are carried out, replacement is carried out repeatedly for three times, 134kg of butadiene and 0.4kg of potassium persulfate are added, the temperature is started to rise to 40 ℃, and the reaction is carried out for 12h. Adjusting the pH value to about 7, adding a terminating agent, adding a defoaming agent, diluting, vacuum degassing until the required solid content is more than 43%, and adding a certain amount of antioxidant and bactericide to obtain a finished product.
And step two, adding 380kg of deionized water, 0.44kg of potassium pyrophosphate, 0.44kg of potassium hydrogen phosphate and 5.5kg of sodium dodecyl benzene sulfonate in sequence according to the weight parts, stirring for 25min, then sequentially adding 1.37kg of tert-dodecyl mercaptan, 148kg of styrene, 8.7kg of methacrylic acid and 2.2kg of butyl acrylate, starting stirring, filling nitrogen, vacuumizing, repeatedly replacing for three times, adding 40kg of butadiene and 0.4kg of potassium persulfate, starting heating to 60 ℃, and reacting for 12h. Adjusting the pH value to about 7, adding a terminating agent, adding a defoaming agent, diluting, vacuum degassing until the required solid content is more than 43%, and adding a certain amount of antioxidant and bactericide to obtain a finished product.
The latex synthesized in the step one and the latex synthesized in the step two are mixed according to the wet ratio (9:3), and the mixed latex is used for testing the performance to prepare the glove.
Comparative example 2
Comparative example 2 is essentially the same as example 1, except that the compounded latex synthesis procedure is different: the temperature is increased to 40 ℃ and the reaction is carried out for 0.75h. Heating to 60 ℃, wherein the pumping speed of the styrene-butadiene oil phase material is 180kg/h, the pumping speed of the first emulsifier material is 60kg/h, the pumping speed of the first initiator material is 18kg/h, and reacting for 1h. And (3) cooling to 40 ℃, continuously adding the mixture by using an injection pump, wherein the injection pump speed of the butyronitrile oil phase material is 160kg/h, the injection pump speed of the second emulsifying agent material is 60kg/h, the injection pump speed of the second initiating agent material is 18kg/h, and reacting for 3h. The above alternating temperature steps were repeated until a latex with 38% solids was synthesized.
Comparative example 3
Comparative example 3 is essentially the same as example 1, except that the hybrid latex synthesis procedure is different: the temperature is increased to 40 ℃ and the reaction is carried out for 0.75h. Heating to 60 ℃, wherein the pumping speed of the butylbenzene oil phase material is 180kg/h, the pumping speed of the first emulsifier material is 60kg/h, the pumping speed of the first initiator material is 18kg/h, and reacting until the butylbenzene reaction material is used up. And (3) cooling to 40 ℃, continuously adding the mixture by using an injection pump, wherein the speed of the butyronitrile oil phase material injection pump is 160kg/h, the speed of the second emulsifying agent material injection pump is 60kg/h, the speed of the second initiating agent material injection pump is 18kg/h, and reacting until the butyronitrile reaction material is used up. A latex having a solids content of 38% was synthesized.
Comparative example 4
Comparative example 4 is essentially the same as example 1, except that the compounded latex synthesis procedure is different: the temperature is increased to 40 ℃ and the reaction is carried out for 0.75h. Heating to 50 ℃, wherein the injection pump speed of the styrene-butadiene oil phase material is 180kg/h, the injection pump speed of the butyronitrile oil phase material is 160kg/h, the injection pump speed of the emulsifier material is 60kg/h, the injection pump speed of the initiator material is 18kg/h, and reacting until the styrene-butadiene reaction material and the butyronitrile oil phase material are used up until the latex with the solid content of 38% is synthesized. Adjusting the pH value of the composite latex to about 7, adding a terminator, adding a defoaming agent, cooling to 45 ℃, transferring to a degassing kettle, carrying out vacuum degassing until the required solid content is more than 43%, and adding a certain amount of antioxidant and bactericide to obtain a finished product.
Comparative example 5
Comparative example 5 is essentially the same as example 1, except that the compounded latex synthesis procedure is different: the temperature is increased to 50 ℃ and the reaction is carried out for 0.75h. Heating to 70 ℃, wherein the injection pump rate of the styrene-butadiene oil phase material is 180kg/h, the injection pump rate of the first emulsifier material is 60kg/h, the injection pump rate of the first initiator material is 18kg/h, and reacting for 0.25h. And (3) cooling to 50 ℃, continuously adding the mixture by using an injection pump, wherein the speed of the injection pump for the butyronitrile oil phase material is 160kg/h, the speed of the injection pump for the second emulsifying agent material is 60kg/h, the speed of the injection pump for the second initiating agent material is 18kg/h, and reacting for 0.75h. Repeating the alternating heating and cooling steps until the composite latex with the solid content of more than 43 percent is synthesized.
Examples of the experiments
The composite latexes provided in examples 1 to 5 and comparative examples 1 to 5 above were examined for solid content, viscosity, pH, particle size, surface tension and mechanical stability, and meanwhile, glove blanks were dipped in the composite latexes provided in examples 1 to 5 and comparative examples 1 to 5 above, and the obtained gloves were tested for glove properties (EN 388), glove abrasion resistance and oil resistance.
Specifically, after the composite latex provided by the above examples 1 to 5 and comparative examples 1 to 5 is vulcanized by a labor insurance abrasive, the chemical fiber knitted glove blank is preheated, and then dipped in the coagulant after the temperature reaches 45 to 55 ℃, wherein the dipping time in the coagulant is 1 to 3 seconds, and the dipping time in the nitrile rubber cement is 2 to 6 seconds. Putting into an oven at 80 deg.C for 30min, heating to 120 deg.C, and oven drying for 1.5h.
The gloves were tested according to the mechanical protection standard EN388 (european standard for protection of industrial gloves).
Oil resistance test: the oil resistance is tested according to the oil resistance test standard AQ-6101-2007 in the national people's republic of China safety production industry Standard:
(1) Before oil immersion treatment
The complete glove was cut out, 4 pieces of type 2 or type 4 test pieces were cut out from the palm, back of hand and sleeve, respectively, as specified in GB/T528-1998, and half of the pieces were measured for tensile properties and hardness before immersion in oil, as specified in GB/T528-1998 and GB/T531-1999.
(2) After oil immersion treatment
And (3) immersing the rest samples cut before the oil immersion treatment in No. 1 standard oil at 23 +/-2 ℃ for 24h, and taking out. The surface was washed with gasoline for 30s, wiped with filter paper and left to stand in air at room temperature for 30min. The tensile properties of the gloves after immersion were then determined as specified in GB/T528-1998.
Oil resistance evaluation standards are distinguished according to technical indexes, and the distinguishing standards refer to a table 4:
TABLE 4 oil resistance evaluation differentiation criteria
| Test items | Superior food | Good wine | In | Difference (D) |
| Tensile strength | ≥9MPa | ≥9MPa | ≥9MPa | ≥9MPa |
| Elongation at break | ≥500 | ≥500 | ≥500 | ≥300 |
| Permanent deformation at break | ≤40% | ≤40% | ≤40% | ≤40% |
| Hardness (Shao Er A) | ＜ 50 | ＜ 50 | ＜ 50 | ＜ 50 |
| Tensile Strength after immersion in Standard oil No. 1 (at 23. + -. 2 ℃ C., 24 h) | ≥20MPa | 13-20MPa | 6.5-13MPa | ≤6.5MPa |
| Elongation at Break after immersion in Standard oil No. 1 (at 23 + -2 deg.C, 24 h) | ≥400 | ≥400 | ≥400 | ≥500 |
The test results are shown in Table 5.
TABLE 5 composite latex-related test results
As can be seen from Table 5, the latex obtained in examples 1 to 5 of the present application and the gloves prepared from the latex were more excellent in properties. In comparative example 1, the latex viscosity, particle size, surface tension and mechanical stability obtained by preparing the nitrile latex and the styrene-butadiene latex separately and then mixing them in a certain ratio were significantly greater than those of the examples of the present application, while the glove performance was significantly inferior to that of the examples of the present application. It can be seen from the data of comparative example 2 that increasing the reaction time of each temperature rise and temperature drop leads to a decrease in product performance, because the reaction time is prolonged, which leads to poor fusion and poor stability of two adjacent layers of butyronitrile and butylbenzene, and further leads to a decrease in performance of the final product. As can be seen from the data of comparative example 3, ding Benceng is molded at one time and the butyronitrile layer is molded outside the butylbenzene layer, comparative example 3 has no multilayer alternating structure and the performance is significantly reduced. The data of comparative example 4 show that the system is complicated in the same time period, the polymer structure is difficult to control, and the product performance is poor when the butyronitrile oil phase material and the butylbenzene oil phase material are added for mixing reaction. As can be seen from the data of comparative example 5, the reaction temperature is higher than the limited range, side reactions such as polymer branching and crosslinking are increased, and the performance is poor.
In summary, the butyronitrile butadiene styrene composite latex for the dipping gloves provided by the application improves the problems of certain defects in brightness and wear resistance and poor cold resistance of the dipping gloves prepared by the existing butyronitrile latex; the styrene-butadiene latex has poor oil resistance and the application range of the glove is limited; according to the butyronitrile butadiene-styrene composite latex for the gum dipping glove, through specific stepwise temperature rising and cooling operations, and when the temperature rises and falls to the reaction temperature each time, a butadiene-styrene oil phase material and a butyronitrile oil phase material are respectively added, and an emulsifier and an initiator are added for mixed reaction, so that a multilayer butyronitrile-butadiene-styrene composite structure is generated; the whole operation process is controllable, and the excellent performance of each layer of sizing material is ensured; the continuous feeding of the injection pump is adopted, so that the core-shell structure of the colloidal particles can be alternately changed, the fusion of two rubber materials in the using process is facilitated, and the stability of a latex system is improved; the composite latex has the advantages of styrene butadiene rubber and nitrile butadiene rubber, has excellent oil resistance, weather resistance, wear resistance and acid and alkali resistance, saves the production cost of gloves, has excellent use value, and plays a positive role in providing a new material for the labor protection industry.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A preparation method of butyronitrile butadiene styrene composite latex for gum dipping gloves is characterized by comprising the following steps:
(1) Uniformly mixing deionized water, electrolyte, a pH buffering agent, an emulsifier component, a molecular weight regulator, acrylonitrile, unsaturated carboxylic acid and unsaturated carboxylic ester, adding butadiene and an initiator component to form an initial reaction material, heating to 35-45 ℃, and reacting for 0.5-0.8h; the mass ratio of deionized water, electrolyte, pH buffer, emulsifier component, unsaturated carboxylic acid, unsaturated carboxylic ester, molecular weight regulator, acrylonitrile, butadiene and initiator component in the initial reaction material is 300-340:0.03-0.06:0.03-0.06:0.3-0.7:0.5-0.9:0-0.3:0.05-0.09:2.5-5:7-10:0.03-0.04;
(2) Heating to 55-65 ℃, adding a butylbenzene oil phase material, a first emulsifying agent material and a first initiator material, and reacting for 0.2-0.5h to form a butylbenzene layer; the butylbenzene oil phase material comprises the following raw materials in a mass ratio of 30-45:0.2-0.4:2-4:0-1.5:8 to 11 of styrene, a molecular weight regulator, unsaturated carboxylic acid, unsaturated carboxylic ester and butadiene;
(3) Cooling to 35-45 ℃, adding the butyronitrile oil phase material, the second emulsifying agent material and the second initiator material, and reacting for 0.5-0.8h to form a butyronitrile layer; the butyronitrile oil phase material comprises the following raw materials in a mass ratio of 30-50:0.5-1.5:6-10:0-3:80 to 100 parts of acrylonitrile, a molecular weight regulator, unsaturated carboxylic acid, unsaturated carboxylic ester and butadiene;
(4) Repeating the step (2) and the step (3) until composite latex with the solid content of 38-40% is synthesized, wherein the composite latex has a composite structure of multilayer butyronitrile and multilayer butylbenzene;
wherein the adding rate of the butylbenzene oil phase material is 160-200kg/h, and the adding rate of the butyronitrile oil phase material is 150-180kg/h;
the raw materials of the first emulsifying agent material and the second emulsifying agent material both comprise, by mass, 50-70:0.3-0.5:0.3-0.5:4-7 deionized water, electrolyte, pH buffer and emulsifier components;
the raw materials of the first initiator charge and the second initiator charge respectively comprise, by mass, 15-25:0.3-0.5 deionized water and an initiator component.
2. The method for preparing the butyronitrile butadiene styrene composite latex for the gum dipping glove according to claim 1, wherein the adding rate of the first emulsifying agent material and the second emulsifying agent material is 55-66kg/h; the first initiator charge and the second initiator charge are each added at a rate of 17 to 20 kg/hour.
3. The method for preparing the butyronitrile butadiene styrene composite latex for the gum dipping glove according to claim 1, wherein the butadiene styrene oil phase material, the butyronitrile oil phase material, the first emulsifier material, the second emulsifier material, the first initiator material and the second initiator material are uniformly added by using an injection pump.
4. The method for preparing the butyronitrile butadiene styrene composite latex for the gum dipping glove according to claim 1, wherein the heating rate of heating to 55-65 ℃ is 2-3 ℃/min, and the cooling rate of cooling to 35-45 ℃ is 3-4 ℃/min.
5. The preparation method of the butyronitrile butadiene styrene composite latex for the gum dipping glove according to claim 1, wherein the electrolyte is one or a mixture of potassium chloride and potassium pyrophosphate;
the pH buffer is one or a mixture of sodium bicarbonate, potassium carbonate or potassium hydrogen phosphate;
the unsaturated carboxylic acid is one or a mixture of methacrylic acid and acrylic acid;
the unsaturated carboxylic ester is one or a mixture of ethyl acrylate, butyl acrylate or ethyl methacrylate;
the emulsifier component is one or a mixture of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, potassium oleate and sodium naphthalene sulfonate;
the molecular weight regulator is one or a mixture of tert-dodecyl mercaptan and diisopropyl xanthogen disulfide;
the initiator component is one or two of potassium persulfate or ammonium persulfate.
6. The method for preparing the butyronitrile butadiene styrene composite latex for the glove dipping according to claim 1, wherein the method for preparing the butyronitrile butadiene styrene composite latex for the glove dipping further comprises degassing and post-treating the composite latex: and adjusting the pH value of the composite latex to 6-8, adding a terminator and a defoaming agent, diluting, vacuum degassing to obtain the required solid content, and adding an antioxidant and a bactericide to obtain the finished product.
7. The butyronitrile butadiene styrene composite latex for the latex gloves is characterized by being prepared by the preparation method of the butyronitrile butadiene styrene composite latex for the latex gloves according to any one of claims 1 to 6.
8. A dipped glove which is characterized in that the glove comprises a glove blank, and the glove blank is dipped with the butyronitrile butadiene styrene composite latex for the dipped glove of claim 7.
9. A preparation method of dipped gloves is characterized in that glove blanks are preheated to 45-55 ℃, dipped with a coagulant for 1-3 seconds and then dipped into the butyronitrile-butylbenzene composite latex for the dipped gloves as claimed in claim 7 for 2-6 seconds, and then the dipped gloves are placed into an oven at 70-90 ℃ for drying for 20-40 min and then heated to 110-130 ℃ for drying for 1-2h.
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| CN114133589A (en) * | 2021-12-27 | 2022-03-04 | 南通强生新材料科技股份有限公司 | Novel butyronitrile butadiene styrene composite latex dipping slurry and preparation method thereof |
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| CN105237682A (en) * | 2015-10-19 | 2016-01-13 | 杭州蓝诚实业有限公司 | Method for preparing high performance carboxylic acrylonitrile butadiene rubber latexes |
| CN108486902A (en) * | 2018-03-13 | 2018-09-04 | 山东星宇手套有限公司 | A kind of graphene overlay film rubber gloves and preparation method thereof |
| WO2021091366A1 (en) * | 2019-11-07 | 2021-05-14 | Kossan Sdn. Bhd. | Polymeric/inorganic composite particle formulation and methods of producing rubber articles using said formulation |
| CN113683728A (en) * | 2021-07-02 | 2021-11-23 | 上海昶法新材料有限公司 | Preparation method of carboxylated butyronitrile latex |
| CN114133589A (en) * | 2021-12-27 | 2022-03-04 | 南通强生新材料科技股份有限公司 | Novel butyronitrile butadiene styrene composite latex dipping slurry and preparation method thereof |
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