CN114591584A - Carbon-filled modified acrylate rubber and composition and preparation method thereof - Google Patents
Carbon-filled modified acrylate rubber and composition and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of acrylate rubber, and particularly relates to a carbon-filled modified acrylate rubber, a composition and a preparation method thereof. The preparation method of the carbon-filled modified acrylate rubber comprises the following steps: carrying out hydrophilic modification on carbon black and dispersing the carbon black in a lauryl sodium sulfate solution to obtain a hydrophilic modified carbon black dispersion liquid; adding sodium dodecyl sulfate, OP-10, sodium hydrosulfite, ethyl acrylate, n-butyl acrylate, methoxyethyl acrylate, hydroxypropyl acrylate, a molecular weight regulator, vinyl chloroacetate and acrylic acid into deionized water for polymerization reaction, adding a hydrophilic modified carbon black dispersion liquid after the reaction is finished, reacting, and then demulsifying, washing and drying to obtain the carbon-filled modified acrylate rubber. The carbon-filled modified acrylate rubber composition has the glass transition temperature of below 43 ℃ below zero and the strength of more than 10MPa, and simultaneously meets the requirements of ultralow temperature and high strength.
Description
Technical Field
The invention belongs to the technical field of acrylate rubber, and particularly relates to a carbon-filled modified acrylate rubber, a composition and a preparation method thereof.
Background
The acrylate rubber is generally composed of a hard monomer, a soft monomer and a vulcanized monomer, wherein the soft monomer directly affects low temperature, and when the soft monomer is added in a large amount, the acrylate rubber has a low glass transition temperature and good low temperature resistance, but when the soft monomer is added in a large amount, the strength of the acrylate rubber is reduced.
Patent CN100369972C discloses a method for preparing a cold-resistant polyacrylate rubber which is easy to process, wherein an acrylate monomer, a low-temperature oil-resistant monomer, a vulcanization point monomer, and a crosslinking monomer are used as comonomers, and a polyacrylate rubber raw rubber is synthesized by an emulsion polymerization method, and is subjected to mixing and vulcanization to prepare a cold-resistant polyacrylate rubber with a pre-crosslinking structure, wherein the glass transition temperature of the cold-resistant polyacrylate rubber can reach-42.3 ℃, the brittleness temperature of the cold-resistant polyacrylate rubber can reach-38 ℃, but the strength of the cold-resistant polyacrylate rubber is only 8.95MPa, and the cold-resistant polyacrylate rubber cannot meet the performance requirements of the market at the present stage, particularly the performance requirements of a turbo-charging pipe on acrylate rubber.
Patent CN107915807A discloses a micro-crosslinked low temperature resistant raw acrylic rubber and a preparation method thereof, which aims to overcome the disadvantages of poor low temperature resistance and poor mechanical properties of the existing acrylic rubber, however, the effect is not ideal, the minimum glass transition temperature of the acrylic rubber prepared by the method is only-25.6 ℃, and the corresponding tensile strength is only 1.91MPa at this time, and is not effectively improved.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: provides a carbon-filled modified acrylate rubber, the glass transition temperature of the composition is below minus 43 ℃, the strength is above 10MPa, and the requirements of ultralow temperature and high strength are met; the invention provides a preparation method thereof.
The preparation method of the carbon-filled modified acrylate rubber comprises the following steps:
(1) preparing a hydrophilic modified carbon black dispersion: mixing carbon black, sodium nitrate and concentrated sulfuric acid, adding potassium perchlorate, mixing uniformly, adding potassium permanganate in batches for oxidation modification to obtain hydrophilic modified carbon black, and dispersing the hydrophilic modified carbon black in a sodium dodecyl sulfate solution to obtain a hydrophilic modified carbon black dispersion liquid;
(2) acrylate raw rubber: adding sodium dodecyl sulfate, OP-10, sodium dithionite, ethyl acrylate, n-butyl acrylate, methoxyethyl acrylate, hydroxypropyl acrylate, a molecular weight regulator, vinyl chloroacetate and acrylic acid into deionized water, mixing at 50-60 ℃, adding an oxidation-reduction initiator after deoxidization, and carrying out polymerization reaction at 70-90 ℃ to obtain raw acrylate rubber;
(3) the method comprises the following steps of (1) carbonizing and modifying a raw acrylate rubber molecular chain: after the polymerization reaction is finished, the temperature of a reaction system is raised to 80-90 ℃, hydrophilic modified carbon black dispersion liquid is added to react for 2-6 hours, and then demulsification, washing and drying are carried out to obtain the carbon-filled modified acrylate rubber.
In the step (1), carbon black with a higher structure is selected for modification, such as N330, N550 and the like.
The dosage ratio of the carbon black, the sodium nitrate and the concentrated sulfuric acid is 5g, (3-4) g, (200-220) mL.
The mass ratio of the potassium perchlorate to the carbon black is 1 (5-6).
The mass ratio of the potassium permanganate to the carbon black is 1 (3-4).
The concentration of the sodium lauryl sulfate solution is 0.5-2%, preferably 1%.
The content of the hydrophilic modified carbon black in the hydrophilic modified carbon black dispersion is 1 to 2mg/ml, preferably 1 mg/ml.
Preferably, the preparation method of the hydrophilic modified carbon black comprises the following steps:
in an ice-water bath, mixing carbon black, sodium nitrate and concentrated sulfuric acid in proportion, adding potassium perchlorate, mixing uniformly, then adding potassium permanganate in batches, controlling the reaction temperature to be lower than 10 ℃, stirring and reacting for 24-48h, then slowly adding deionized water, heating to 95-98 ℃, stirring for 30-50min, then adding hydrogen peroxide to reduce residual oxidant, carrying out suction filtration while hot, washing with dilute hydrochloric acid and deionized water successively until the pH value of a separation solution is 5-6, and carrying out freeze drying on the obtained dispersion solution after ultrasonic dispersion to obtain the hydrophilic modified carbon black.
In one embodiment, the hydrophilic modified carbon black is prepared by the following method: in an ice-water bath, uniformly mixing 5g of carbon black, 3g of sodium nitrate and 220ml of concentrated sulfuric acid, adding 30g of potassium perchlorate while stirring, after uniformly mixing, adding 15g of potassium permanganate in batches, controlling the temperature to be not more than 10 ℃, stirring for 30min, removing an ice bath, and continuously stirring for 48h by magnetic force; slowly adding 300ml of deionized water 8 times, raising the temperature to about 98 ℃, stirring for 40min, adding hydrogen peroxide to reduce the residual oxidant, carrying out suction filtration while the mixture is hot, and washing the mixture with a 5% HCl solution and deionized water successively until the pH value of a separation solution is 5-6; and ultrasonically dispersing the obtained dispersion liquid for 1h, and then carrying out freeze drying to obtain the hydrophilic modified carbon black.
In the step (2), the raw materials are counted by weight:
0.02-0.03 part of oxidation-reduction initiator.
Among them, the molecular weight regulator is preferably one or more of dodecanethiol and diisopropyl xanthogen disulfide.
The oxidation-reduction initiator consists of an oxidizing agent and a reducing agent with the same mass; wherein the oxidant is preferably one or more of hydrogen peroxide, sodium persulfate, potassium persulfate and cumene hydroperoxide; the reducing agent is preferably one or more of ferrous sulfate, sodium formaldehyde sulfoxylate, sodium bisulfite, sodium sulfite and sodium thiosulfate.
In the step (3), the carbon-filling modification is to modify the molecular chain of the raw acrylate rubber by modified carbon black. The amount of the hydrophilic modified carbon black dispersion is 0.002-0.02% of the mass of the raw acrylate rubber based on the hydrophilic modified carbon black contained in the dispersion.
The invention also provides a composition of the carbon-filled modified acrylate rubber, which comprises the following raw materials in parts by weight:
wherein the carbon black is N330 or N550.
The stearic acid has the function of lubricating and improving the processability of the rubber compound.
KY445 is preferably selected as the antioxidant, and the antioxidant has the function of improving the aging resistance of the rubber compound.
The internal mold release agent is preferably 18D, and functions to improve the mold releasability of the rubber composition.
The polyester plasticizer is preferably RS107, and has the function of improving the flowability of the rubber compound.
The sodium stearate acts as a vulcanization accelerator to promote the activation of the vulcanizing agent, thereby accelerating the crosslinking reaction of the vulcanizing agent with rubber molecules.
The vulcanizing agent is preferably NPC-50, and has the function of carrying out crosslinking reaction with rubber molecules.
The invention also provides a preparation method of the composition, which comprises the following steps:
putting the carbon-filled modified acrylate rubber, stearic acid, an antioxidant, an internal release agent, a polyester plasticizer and carbon black into an internal mixer, carrying out internal mixing for 10-20min at 50-60 ℃, taking out, putting into an open mill, adjusting the roll distance of the open mill to 2-3mm, adding sodium stearate and a vulcanizing agent into the open mill, and after complete mixing, packaging in a triangular bag and taking out the sheet.
Compared with the prior art, the invention has the following beneficial effects:
the molecular chain of the raw acrylate rubber is modified by the modified carbon black, so that the obtained carbon-filled modified acrylate rubber has the glass transition temperature of below 43 ℃ below zero and the strength of above 10MPa, meets the requirements of ultralow temperature and high strength, and meets the use requirements of the acrylate rubber at extremely cold temperature.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the invention is not limited thereto. The starting materials used in the examples are, unless otherwise specified, commercially available conventional starting materials; how the methods used in the examples are specifically illustrated is a routine method in the art.
Example 1
(1) Preparing a modified carbon black dispersion:
a500 ml reaction bottle is assembled in an ice-water bath, 5g N330, 3g of sodium nitrate and 220ml of concentrated sulfuric acid are uniformly mixed, 30g of potassium perchlorate is added under stirring, after the mixture is uniform, 15g of potassium permanganate is added for multiple times, the temperature is controlled not to exceed 10 ℃, after stirring for 30min, the ice bath is removed, the reaction bottle is transferred to a magnetic stirrer, and magnetic stirring lasts for 48 h. Then slowly adding 300ml of deionized water for 8 times, raising the temperature to about 98 ℃, stirring for 40min, and adding a proper amount of hydrogen peroxide to reduce the residual oxidant. And (4) carrying out suction filtration while the solution is hot, and washing the solution by using a 5% HCl solution and deionized water sequentially until the pH value of a separation solution is 5-6. And ultrasonically dispersing the obtained dispersion liquid for 1h, and then carrying out freeze drying to obtain the hydrophilic modified N330. A1 mg/ml hydrophilic modified N330 dispersion was prepared using a 1% sodium lauryl sulfate solution as the dispersion.
(2) Preparing the carbon-filled modified acrylate rubber:
fully mixing the following raw materials in parts by weight at 55 ℃, introducing nitrogen to remove oxygen for 30min, adding an oxidation-reduction initiator (sodium persulfate and sodium formaldehyde sulfoxylate in a mass ratio of 1: 1) to start a polymerization reaction, keeping the system temperature at 80 ℃, carrying out the polymerization reaction to obtain raw acrylate rubber, raising the system temperature to 90 ℃ after the polymerization reaction is finished, adding a hydrophilic modified N330 dispersion liquid with the mass of 0.002% (based on the mass of hydrophilic modified N330 contained in the dispersion liquid) of the raw acrylate rubber, reacting for 4h, demulsifying, washing and drying to obtain the carbon-filled modified acrylate rubber;
(3) preparation of the composition:
putting the following raw materials into an internal mixer according to a ratio by weight, internally mixing for 15min at 60 ℃, taking out the composition, adjusting the roll gap of an open mill to 2mm, adding 4 parts of sodium stearate and 2 parts of NPC-50 into the open mill, beating for 6 times to form a triangular bag after complete mixing, and discharging;
example 2
(1) Preparing a modified carbon black dispersion:
and (2) assembling a 500ml reaction bottle in an ice-water bath, uniformly mixing 5g of N330, 4g of sodium nitrate and 200ml of concentrated sulfuric acid, adding 25g of potassium perchlorate while stirring, adding 20g of potassium permanganate again after uniform mixing, controlling the temperature to be not more than 10 ℃, removing the ice bath after stirring for 30min, transferring the reaction bottle to a magnetic stirrer, and continuing magnetic stirring for 36 h. Then slowly adding 300ml of deionized water for 8 times, raising the temperature to about 95 ℃, stirring for 50min, and adding a proper amount of hydrogen peroxide to reduce the residual oxidant. And (4) carrying out suction filtration while the solution is hot, and washing the solution by using a 5% HCl solution and deionized water sequentially until the pH value of a separation solution is 5-6. And ultrasonically dispersing the obtained dispersion liquid for 1h, and then carrying out freeze drying to obtain the hydrophilic modified N330. A2 mg/ml dispersion of hydrophilically modified N330 was prepared using a 1% sodium lauryl sulfate solution as the dispersion.
(2) Preparing the carbon-filled modified acrylate rubber:
according to the weight parts, the following raw materials are fully mixed according to the proportion at 50 ℃, nitrogen is introduced for deoxidizing for 30min, then an oxidation-reduction initiator (potassium persulfate and ferrous sulfate in a mass ratio of 1: 1) is added to initiate polymerization, the system temperature is kept at 70 ℃, the polymerization reaction is carried out to obtain raw acrylate rubber, the system temperature is raised to 90 ℃ after the polymerization reaction is finished, then hydrophilic modified N330 dispersion liquid with the mass of 0.008 percent (based on the mass of hydrophilic modified N330 contained in the dispersion liquid) of the raw acrylate rubber is added to react for 4h, and then demulsification, washing and drying are carried out to obtain the carbon-filled modified acrylate rubber;
(3) preparation of the composition:
putting the following raw materials into an internal mixer according to a ratio by weight, internally mixing for 15min at 60 ℃, taking out the composition, adjusting the roll gap of an open mill to 2mm, adding 4.5 parts of sodium stearate and 1.5 parts of NPC-50 into the open mill, stirring for 6 times of triangular bags after complete mixing, and discharging;
example 3
(1) Preparing a modified carbon black dispersion liquid:
a500 ml reaction bottle is assembled in an ice-water bath, 5g N330, 3.5g of sodium nitrate and 210ml of concentrated sulfuric acid are uniformly mixed, 28g of potassium perchlorate is added under stirring, 18g of potassium permanganate is added for multiple times after the mixture is uniform, the temperature is controlled not to exceed 10 ℃, after stirring is carried out for 30min, the ice bath is removed, the reaction bottle is transferred to a magnetic stirrer, and magnetic stirring is carried out for 48 h. Then slowly adding 300ml of deionized water for 8 times, raising the temperature to about 98 ℃, stirring for 40min, and adding a proper amount of hydrogen peroxide to reduce the residual oxidant. And (4) carrying out suction filtration while the solution is hot, and washing the solution by using a 5% HCl solution and deionized water sequentially until the pH value of a separation solution is 5-6. And ultrasonically dispersing the obtained dispersion liquid for 1h, and then carrying out freeze drying to obtain the hydrophilic modified N330. A1.5 mg/ml dispersion of hydrophilically modified N330 was prepared using a 2% sodium lauryl sulfate solution as the dispersion.
(2) Preparing the carbon-filled modified acrylate rubber:
fully mixing the following raw materials in parts by weight at 60 ℃, introducing nitrogen to remove oxygen for 30min, adding an oxidation-reduction initiator (sodium persulfate and sodium formaldehyde sulfoxylate in a mass ratio of 1: 1) to start a polymerization reaction, keeping the system temperature at 90 ℃, carrying out the polymerization reaction to obtain raw acrylate rubber, keeping the system temperature at 90 ℃ after the polymerization reaction is finished, adding a hydrophilic modified N330 dispersion liquid with the mass of 0.012% (based on the mass of hydrophilic modified N330 contained in the dispersion liquid) of the raw acrylate rubber, carrying out a reaction for 4h, and carrying out demulsification, washing and drying to obtain the carbon-filled modified acrylate rubber;
(3) preparation of the composition:
putting the following raw materials into an internal mixer according to a ratio by weight, internally mixing for 15min at 60 ℃, taking out the composition, adjusting the roll gap of an open mill to 2mm, adding 3.5 parts of sodium stearate and 2.5 parts of NPC-50 into the open mill, stirring for 6 times of triangular bags after complete mixing, and discharging;
example 4
(1) Preparing a modified carbon black dispersion:
a500 ml reaction bottle is assembled in an ice-water bath, 5g N330, 3g of sodium nitrate and 220ml of concentrated sulfuric acid are uniformly mixed, 30g of potassium perchlorate is added under stirring, after the mixture is uniform, 15g of potassium permanganate is added for multiple times, the temperature is controlled not to exceed 10 ℃, after stirring for 30min, the ice bath is removed, the reaction bottle is transferred to a magnetic stirrer, and magnetic stirring lasts for 48 h. Then slowly adding 300ml of deionized water for 8 times, raising the temperature to about 98 ℃, stirring for 40min, and adding a proper amount of hydrogen peroxide to reduce the residual oxidant. And (4) carrying out suction filtration while the solution is hot, and washing the solution by using a 5% HCl solution and deionized water sequentially until the pH value of a separation solution is 5-6. And ultrasonically dispersing the obtained dispersion liquid for 1h, and then carrying out freeze drying to obtain the hydrophilic modified N330. A1 mg/ml dispersion of hydrophilically modified N330 was prepared using a 0.5% sodium lauryl sulfate solution as the dispersion.
(2) Preparing the carbon-filled modified acrylate rubber:
according to the weight parts, the following raw materials are fully mixed according to the proportion at 55 ℃, nitrogen is introduced for deoxidizing for 30min, then an oxidation-reduction initiator (sodium persulfate and sodium formaldehyde sulfoxylate in a mass ratio of 1: 1) is added to initiate polymerization, the system temperature is kept at 70 ℃, the polymerization reaction is carried out to obtain raw acrylate rubber, the system temperature is raised to 80 ℃ after the polymerization reaction is finished, then hydrophilic modified N330 dispersion liquid with the mass of 0.016% (based on the mass of hydrophilic modified N330 contained in the dispersion liquid) is added to react for 6h, and then demulsification, washing and drying are carried out to obtain the charcoaling modified acrylate rubber;
(3) preparation of the composition:
putting the following raw materials into an internal mixer according to a ratio by weight, internally mixing for 15min at 60 ℃, taking out the composition, adjusting the roll gap of an open mill to 2mm, adding 3.8 parts of sodium stearate and 2.2 parts of NPC-50 into the open mill, stirring for 6 times of triangular bags after complete mixing, and discharging;
example 5
(1) Preparing a modified carbon black dispersion:
a500 ml reaction bottle is assembled in an ice-water bath, 5g N330, 3g of sodium nitrate and 220ml of concentrated sulfuric acid are uniformly mixed, 30g of potassium perchlorate is added under stirring, after the mixture is uniform, 15g of potassium permanganate is added for multiple times, the temperature is controlled not to exceed 10 ℃, after stirring for 30min, the ice bath is removed, the reaction bottle is transferred to a magnetic stirrer, and magnetic stirring lasts for 48 h. Then slowly adding 300ml of deionized water for 8 times, raising the temperature to about 98 ℃, stirring for 40min, and adding a proper amount of hydrogen peroxide to reduce the residual oxidant. And (4) carrying out suction filtration while the solution is hot, and washing the solution by using a 5% HCl solution and deionized water sequentially until the pH value of a separation solution is 5-6. And ultrasonically dispersing the obtained dispersion liquid for 1h, and then carrying out freeze drying to obtain the hydrophilic modified N330. A1.5% sodium lauryl sulfate solution was used as a dispersion to prepare a 1mg/ml dispersion of hydrophilically modified N330.
(2) Preparing the carbon-filled modified acrylate rubber:
fully mixing the following raw materials in parts by weight at 55 ℃, introducing nitrogen to remove oxygen for 30min, adding an oxidation-reduction initiator (sodium persulfate and sodium formaldehyde sulfoxylate in a mass ratio of 1: 1) to initiate a polymerization reaction, keeping the system temperature at 80 ℃, performing the polymerization reaction to obtain raw acrylate rubber, raising the system temperature to 90 ℃ after the polymerization reaction is finished, adding a hydrophilic modified N330 dispersion liquid which is 0.02% of the mass of the raw acrylate rubber (based on the mass of hydrophilic modified N330 contained in the dispersion liquid), reacting for 3h, demulsifying, washing and drying to obtain the carbon-filled modified acrylate rubber;
(3) preparation of the composition:
putting the following raw materials into an internal mixer according to a ratio by weight, internally mixing for 20min at 50 ℃, taking out the composition, adjusting the roll gap of an open mill to 3mm, adding 4 parts of sodium stearate and 2 parts of NPC-50 into the open mill, beating for 6 times to form a triangular bag after complete mixing, and discharging;
example 6
(1) Preparing a modified carbon black dispersion:
a500 ml reaction bottle is assembled in an ice-water bath, 5g N550, 3g of sodium nitrate and 220ml of concentrated sulfuric acid are uniformly mixed, 30g of potassium perchlorate is added under stirring, after the mixture is uniform, 15g of potassium permanganate is added for multiple times, the temperature is controlled not to exceed 10 ℃, after stirring for 30min, the ice bath is removed, the reaction bottle is transferred to a magnetic stirrer, and magnetic stirring lasts for 48 h. Then slowly adding 300ml of deionized water for 8 times, raising the temperature to about 98 ℃, stirring for 40min, and adding a proper amount of hydrogen peroxide to reduce the residual oxidant. And (4) carrying out suction filtration while the solution is hot, and washing the solution by using a 5% HCl solution and deionized water sequentially until the pH value of a separation solution is 5-6. And ultrasonically dispersing the obtained dispersion liquid for 1h, and then carrying out freeze drying to obtain the hydrophilic modified N550. A1 mg/ml hydrophilically modified N550 dispersion was prepared using a 1% sodium lauryl sulfate solution as the dispersion.
(2) Preparing the carbon-filled modified acrylate rubber:
fully mixing the following raw materials in parts by weight at 55 ℃, introducing nitrogen to remove oxygen for 30min, adding an oxidation-reduction initiator (sodium persulfate and sodium formaldehyde sulfoxylate in a mass ratio of 1: 1) to start a polymerization reaction, keeping the system temperature at 80 ℃, performing the polymerization reaction to obtain raw acrylate rubber, raising the system temperature to 90 ℃ after the polymerization reaction is finished, adding a hydrophilic modified N550 dispersion liquid which is 0.016 percent by mass of the raw acrylate rubber (based on the mass of hydrophilic modified N550 contained in the dispersion liquid), reacting for 4h, demulsifying, washing and drying to obtain the carbon-filled modified acrylate rubber;
(3) preparation of the composition:
putting the following raw materials into an internal mixer according to a ratio by weight, internally mixing for 10min at 55 ℃, taking out the composition, adjusting the roll gap of an open mill to 2mm, adding 4 parts of sodium stearate and 2 parts of NPC-50 into the open mill, beating for 6 times to form a triangular bag after complete mixing, and discharging;
comparative example 1
Compared with the example 1, the preparation method of the comparative example adopts raw acrylate rubber to replace the carbon-filled modified acrylate rubber and comprises the following steps:
(1) preparing raw acrylate rubber:
according to the weight parts, the following raw materials are fully mixed according to the proportion at 55 ℃, nitrogen is introduced for deoxidizing for 30min, then an oxidation-reduction initiator (sodium persulfate and sodium formaldehyde sulfoxylate with the mass ratio of 1: 1) is added to initiate polymerization reaction, the system temperature is kept at 80 ℃, and the raw acrylate rubber is obtained through polymerization reaction;
(2) preparation of the composition:
putting the following raw materials into an internal mixer according to a ratio by weight, internally mixing for 15min at 60 ℃, taking out the composition, adjusting the roll gap of an open mill to 2mm, adding 4 parts of sodium stearate and 2 parts of NPC-50 into the open mill, beating for 6 times to form a triangular bag after complete mixing, and discharging;
comparative example 2
Compared with the example 1, the preparation method of the comparative example, which adopts the raw acrylate rubber to replace the carbon-filled modified acrylate rubber, comprises the following steps:
(1) preparing raw acrylate rubber:
according to the weight parts, the following raw materials are fully mixed according to the proportion at 55 ℃, nitrogen is introduced for deoxidizing for 30min, then an oxidation-reduction initiator (sodium persulfate and sodium formaldehyde sulfoxylate with the mass ratio of 1: 1) is added to initiate polymerization reaction, the system temperature is kept at 80 ℃, and the raw acrylate rubber is obtained through polymerization reaction;
(2) preparation of the composition:
putting the following raw materials into an internal mixer according to a ratio by weight, internally mixing for 15min at 60 ℃, taking out the composition, adjusting the roll gap of an open mill to 2mm, adding 4 parts of sodium stearate and 2 parts of NPC-50 into the open mill, beating for 6 times to form a triangular bag after complete mixing, and discharging;
comparative example 3
Compared with the example 1, the preparation method of the comparative example reduces the using amount of the modified carbon black dispersion liquid in the carbon-filled modified acrylate rubber and comprises the following steps:
(1) preparing a modified carbon black dispersion liquid:
a500 ml reaction bottle is assembled in an ice-water bath, 5g N330, 3g of sodium nitrate and 220ml of concentrated sulfuric acid are uniformly mixed, 30g of potassium perchlorate is added under stirring, after the mixture is uniform, 15g of potassium permanganate is added for multiple times, the temperature is controlled not to exceed 10 ℃, after stirring for 30min, the ice bath is removed, the reaction bottle is transferred to a magnetic stirrer, and magnetic stirring lasts for 48 h. Then slowly adding 300ml of deionized water for 8 times, raising the temperature to about 98 ℃, stirring for 40min, and adding a proper amount of hydrogen peroxide to reduce the residual oxidant. And (4) carrying out suction filtration while the solution is hot, and washing the solution by using a 5% HCl solution and deionized water sequentially until the pH value of a separation solution is 5-6. And ultrasonically dispersing the obtained dispersion liquid for 1h, and then carrying out freeze drying to obtain the hydrophilic modified N330. A1 mg/ml hydrophilic modified N330 dispersion was prepared using a 1% sodium lauryl sulfate solution as the dispersion.
(2) Preparing the carbon-filled modified acrylate rubber:
fully mixing the following raw materials in parts by weight at 55 ℃, introducing nitrogen to remove oxygen for 30min, adding an oxidation-reduction initiator (sodium persulfate and sodium formaldehyde sulfoxylate in a mass ratio of 1: 1) to initiate a polymerization reaction, keeping the system temperature at 80 ℃, performing the polymerization reaction to obtain raw acrylate rubber, raising the system temperature to 90 ℃ after the polymerization reaction is finished, adding a hydrophilic modified N330 dispersion liquid which is 0.001% of the mass of the raw acrylate rubber (based on the mass of hydrophilic modified N330 contained in the dispersion liquid), reacting for 4h, demulsifying, washing and drying to obtain the carbon-filled modified acrylate rubber;
(3) preparation of the composition:
putting the following raw materials into an internal mixer according to a ratio by weight, internally mixing for 15min at 60 ℃, taking out the composition, adjusting the roll gap of an open mill to 2mm, adding 4 parts of sodium stearate and 2 parts of NPC-50 into the open mill, beating for 6 times to form a triangular bag after complete mixing, and discharging;
comparative example 4
Compared with the example 1, the preparation method of the comparative example reduces the using amount of the modified carbon black dispersion liquid in the carbon-filled modified acrylate rubber and comprises the following steps:
(1) preparing a modified carbon black dispersion liquid:
a500 ml reaction bottle is assembled in an ice-water bath, 5g N330, 3g of sodium nitrate and 220ml of concentrated sulfuric acid are uniformly mixed, 30g of potassium perchlorate is added under stirring, after the mixture is uniform, 15g of potassium permanganate is added for multiple times, the temperature is controlled not to exceed 10 ℃, after stirring for 30min, the ice bath is removed, the reaction bottle is transferred to a magnetic stirrer, and magnetic stirring lasts for 48 h. Then slowly adding 300ml of deionized water for 8 times, raising the temperature to about 98 ℃, stirring for 40min, and adding a proper amount of hydrogen peroxide to reduce the residual oxidant. And (4) carrying out suction filtration while the solution is hot, and washing the solution by using a 5% HCl solution and deionized water sequentially until the pH value of a separation solution is 5-6. And ultrasonically dispersing the obtained dispersion liquid for 1h, and then carrying out freeze drying to obtain the hydrophilic modified N330. A1 mg/ml hydrophilic modified N330 dispersion was prepared using a 1% sodium lauryl sulfate solution as the dispersion.
(2) Preparing the carbon-filled modified acrylate rubber:
fully mixing the following raw materials in parts by weight at 55 ℃, introducing nitrogen to remove oxygen for 30min, adding an oxidation-reduction initiator (sodium persulfate and sodium formaldehyde sulfoxylate in a mass ratio of 1: 1) to initiate a polymerization reaction, keeping the system temperature at 80 ℃, performing the polymerization reaction to obtain raw acrylate rubber, raising the system temperature to 90 ℃ after the polymerization reaction is finished, adding a hydrophilic modified N330 dispersion liquid which is 0.03 percent of the mass of the raw acrylate rubber (based on the mass of hydrophilic modified N330 contained in the dispersion liquid), reacting for 4h, demulsifying, washing and drying to obtain the carbon-filled modified acrylate rubber;
(3) preparation of the composition:
putting the following raw materials into an internal mixer according to a ratio by weight, internally mixing for 15min at 60 ℃, taking out the composition, adjusting the roll gap of an open mill to 2mm, adding 4 parts of sodium stearate and 2 parts of NPC-50 into the open mill, beating for 6 times to form a triangular bag after complete mixing, and discharging;
the acrylate rubber compositions prepared in examples 1 to 6 and comparative examples 1 to 4 were subjected to a performance test by the following methods:
(1) latex coagulation Rate (m)c)：mcCan reflect the reaction stability of latexcThe smaller the reaction, the better the stability of the reaction, mcThe larger the size, the less stable the reaction process, mcIs obtained by a weighing method, the condensate in a polymerization system is collected after the reaction is finished, and the mass w of the condensate is obtained by drying the condensate in an oven to constant weight at 90 DEG Cc，mc＝wc/wm100%, wherein: m iscCoagulation rate,%; w is acMass of the condensate, g; w is amIs the total mass of the monomers, g.
(2) Mooney viscosity: the measurement of part 1 was carried out according to GB/T1232.1-2016 unvulcanized rubber using a disc shear viscometer: determination of Mooney viscosity.
(3) Glass transition temperature: the test is carried out according to GB/T29611-2013 measurement differential scanning calorimetry for the glass transition temperature of the raw rubber, wherein the heating rate is 10 k/min.
(4) Brittle temperature: the test was carried out according to GB/T15256-.
(5) Tensile strength: the test is carried out according to GB/T528-2009 determination of tensile stress strain performance of vulcanized rubber or thermoplastic rubber, wherein the test sample is a dumbbell type 1 test sample.
(6) Elongation at break: the test is carried out according to GB/T528-2009 determination of tensile stress strain performance of vulcanized rubber or thermoplastic rubber, wherein the test sample is a dumbbell type 1 test sample.
(7) Permanent deformation at breaking: the test is carried out according to GB/T528-2009 determination of tensile stress strain performance of vulcanized rubber or thermoplastic rubber, wherein the test sample is a dumbbell type 1 test sample.
(8) Compression set: determination of compression set according to GB/T7759.1-2015 determination of compression set of vulcanizates or thermoplastic rubbers part 1: the test was performed under normal temperature and high temperature conditions, and the type B test method a was selected, and the test conditions were 150 ℃ for 70 hours.
The test results are shown in table 1:
table 1 results of performance testing
As can be seen from Table 1, the Mooney viscosity of the modified acrylate rubber of comparative examples 1 to 3 is lower than 20, the modified acrylate rubber is abnormally adhered to a roller during processing, the processability is poor, the strength is low, the coagulation rate of the latex of comparative example 4 reaches 0.4%, the reaction stability is poor, the content of coagulated matters is high, the stirring slurry and the reaction kettle are seriously coated with glue, and frequent cleaning is needed, the glass transition temperature of the carbonized modified acrylate rubber composition prepared by the examples 1 to 3 of the invention is lower than minus 43 ℃, the strength is higher than 10MPa, the use of the acrylate rubber at extremely cold temperature is met, and meanwhile, the coagulation rate of the latex is low, thereby being beneficial to industrial production.
Claims (10)
1. A preparation method of carbon-filled modified acrylate rubber is characterized by comprising the following steps: the method comprises the following steps:
(1) preparing a hydrophilic modified carbon black dispersion: mixing carbon black, sodium nitrate and concentrated sulfuric acid, adding potassium perchlorate, mixing uniformly, adding potassium permanganate in batches for oxidation modification to obtain hydrophilic modified carbon black, and dispersing the hydrophilic modified carbon black in a sodium dodecyl sulfate solution to obtain a hydrophilic modified carbon black dispersion liquid;
(2) acrylate raw rubber: adding sodium dodecyl sulfate, OP-10, sodium hydrosulfite, ethyl acrylate, n-butyl acrylate, methoxyethyl acrylate, hydroxypropyl acrylate, a molecular weight regulator, vinyl chloroacetate and acrylic acid into deionized water, mixing at 50-60 ℃, adding an oxidation-reduction initiator after removing oxygen, and carrying out polymerization reaction at 70-90 ℃ to obtain raw acrylate rubber;
(3) the molecular chain of the raw acrylic rubber is carbonized and modified: after the polymerization reaction is finished, the temperature of a reaction system is raised to 80-90 ℃, hydrophilic modified carbon black dispersion liquid is added to react for 2-6 hours, and then demulsification, washing and drying are carried out to obtain the carbon-filled modified acrylate rubber.
2. The method for preparing a carbon-charged modified acrylate rubber according to claim 1, wherein: in the step (1), the content of the hydrophilic modified carbon black in the hydrophilic modified carbon black dispersion liquid is 1-2 mg/ml.
3. The method for preparing a carbon-charged modified acrylate rubber according to claim 1, wherein: in the step (1), the preparation method of the hydrophilic modified carbon black comprises the following steps:
in an ice-water bath, mixing carbon black, sodium nitrate and concentrated sulfuric acid in proportion, adding potassium perchlorate, mixing uniformly, then adding potassium permanganate in batches, controlling the reaction temperature to be lower than 10 ℃, stirring and reacting for 24-48h, then slowly adding deionized water, heating to 95-98 ℃, stirring for 30-50min, then adding hydrogen peroxide to reduce residual oxidant, carrying out suction filtration while hot, washing with dilute hydrochloric acid and deionized water successively until the pH value of a separation solution is 5-6, and carrying out freeze drying on the obtained dispersion solution after ultrasonic dispersion to obtain the hydrophilic modified carbon black.
4. The method for producing a carbon-charged modified acrylate rubber according to claim 3, characterized in that: the dosage ratio of the carbon black, the sodium nitrate and the concentrated sulfuric acid is 5g, (3-4) g, (200-220) mL; the mass ratio of the potassium perchlorate to the carbon black is 1 (5-6); the mass ratio of the potassium permanganate to the carbon black is 1 (3-4).
5. The method for preparing a carbon-charged modified acrylate rubber according to claim 1, wherein: in the step (2), the raw materials are counted by weight:
6. the method for producing a carbon-charged modified acrylate rubber according to claim 5, characterized in that: the molecular weight regulator is preferably one or more of dodecyl mercaptan and diisopropyl xanthogen disulfide;
the oxidation-reduction initiator consists of an oxidizing agent and a reducing agent with the same mass; wherein the oxidant is one or more of hydrogen peroxide, sodium persulfate, potassium persulfate and cumene hydroperoxide; the reducing agent is one or more of ferrous sulfate, sodium bisulfate, sodium sulfite and sodium thiosulfate.
7. The method for preparing a carbon-charged modified acrylate rubber according to claim 1, wherein: in the step (3), the amount of the hydrophilic modified carbon black dispersion liquid is calculated by the hydrophilic modified carbon black contained in the dispersion liquid, and the amount of the hydrophilic modified carbon black is 0.002-0.02% of the mass of the raw acrylate rubber.
8. The carbon-filled modified acrylate rubber is characterized in that: prepared by the preparation method of any one of claims 1 to 7.
9. A composition of the carbon-filled modified acrylate rubber of claim 1 wherein: the composite material comprises the following raw materials in parts by weight:
10. a method for preparing the carbon-filled modified acrylate rubber composition according to claim 9, characterized in that: the method comprises the following steps:
adding the carbon-filled modified acrylate rubber, stearic acid, an antioxidant, an internal release agent, a polyester plasticizer and carbon black into an internal mixer, carrying out internal mixing for 10-20min at 50-60 ℃, taking out, putting into an open mill, adjusting the roll distance of the open mill to 2-3mm, adding sodium stearate and a vulcanizing agent into the open mill, and after completely mixing, packaging in a triangular bag and discharging.
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| JP2000248139A (en) * | 1999-03-02 | 2000-09-12 | Denki Kagaku Kogyo Kk | Acrylic rubber composition |
| CN1861678A (en) * | 2006-05-19 | 2006-11-15 | 北京化工大学 | Preparation process of easy processing cold resisting type polyacrylate rubber |
| KR20130098066A (en) * | 2012-02-27 | 2013-09-04 | 한국기술교육대학교 산학협력단 | Acrylic rubber and acrylic rubber composition comprising the same |
| CN106634059A (en) * | 2016-12-16 | 2017-05-10 | 江南大学 | Preparation method of aqueous self-dispersing nanometer carbon black |
| CN110734594A (en) * | 2018-07-19 | 2020-01-31 | 中国石油天然气股份有限公司 | Method for preparing emulsion polymerized styrene butadiene rubber from modified carbon blacks |
| CN111410855A (en) * | 2019-12-31 | 2020-07-14 | 宁波德泰化学有限公司 | Preparation method of high-surface-activity/high-hydrophilicity dispersion type carbon black |
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| JP2000248139A (en) * | 1999-03-02 | 2000-09-12 | Denki Kagaku Kogyo Kk | Acrylic rubber composition |
| CN1861678A (en) * | 2006-05-19 | 2006-11-15 | 北京化工大学 | Preparation process of easy processing cold resisting type polyacrylate rubber |
| KR20130098066A (en) * | 2012-02-27 | 2013-09-04 | 한국기술교육대학교 산학협력단 | Acrylic rubber and acrylic rubber composition comprising the same |
| CN106634059A (en) * | 2016-12-16 | 2017-05-10 | 江南大学 | Preparation method of aqueous self-dispersing nanometer carbon black |
| CN110734594A (en) * | 2018-07-19 | 2020-01-31 | 中国石油天然气股份有限公司 | Method for preparing emulsion polymerized styrene butadiene rubber from modified carbon blacks |
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