CN116410549A - Anti-blooming full-vulcanization system dispersion master batch - Google Patents
Anti-blooming full-vulcanization system dispersion master batch Download PDFInfo
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Abstract
The invention provides a spray-resistant full-vulcanization system dispersion master batch which comprises the following raw material components in parts by weight: 100 parts of polyisobutene, 300-1000 parts of a rubber accelerator and 100-2000 parts of sulfur; the dispersion master batch is prepared by the following method: and (3) blending the polyisobutene, the rubber accelerator and sulfur, granulating to obtain primary master batches, and heating and curing the primary master batches to obtain the dispersed master batches. The full-vulcanization system dispersion master batch has anti-frosting capability, and can solve the problems that the existing powder auxiliary agent has serious dust and the existing auxiliary agent master batch has single function.
Description
Technical Field
The invention relates to the field of full-vulcanization system dispersion master batches, in particular to an anti-blooming full-vulcanization system dispersion master batch.
Background
CN201810961109.X discloses a rubber compound additive particle, which comprises the following components in parts by weight: 20-30 parts of rubber, 5-8 parts of zinc oxide, 3-5 parts of stearic acid, 4-6 parts of an anti-aging agent, 0.5-1 part of a scorch retarder, 3-5 parts of an accelerator and 2-4 parts of a vulcanizing agent, wherein the particles are cylindrical with the diameter of 2-5 mm and the height of 5-10 mm. The rubber compound additive particle provided by the invention has the functions of an activating agent, an anti-aging agent, an accelerator, a vulcanizing agent and a scorch retarder, can achieve the same effect as the traditional production process by using a small amount of additives, and meanwhile, the multifunctional rubber compound additive particle is a particle master batch particle, so that on one hand, the dispersing effect of various rubber additives in rubber can be effectively improved, on the other hand, the material is convenient to prepare, the weighing error is reduced, the pollution of dust in production to the environment is reduced, and the health of operators is benefited. However, the method simply combines and mixes the auxiliary agents, the rubber content is high, and the effective content of the auxiliary agents is low.
CN201611139624.7 discloses a fluororubber multifunctional puffing auxiliary granule and a preparation method thereof, the fluororubber multifunctional puffing auxiliary comprises the following components: fluororubber, foaming agent, foam stabilizer, vulcanizing agent, acid absorber, reinforcing agent, scorch retarder and release agent. The preparation method is simple and easy to operate, and comprises the following steps: the prepared fluororubber multifunctional puffing auxiliary agent is not agglomerated at room temperature, is easy to mix, has good dispersibility, reduces mixing time, does not fly dust, does not cause skin allergy of operators, and has high raw material utilization rate; after the ingredients are mixed, the ingredients are uniformly dispersed in the rubber product, so that the production efficiency and quality of the rubber product can be ensured, and the method has important significance for sustainable development of rubber manufacturing industry. However, this method does not take care of the full cure system, the cure system pretreatment, and the anti-blooming function of the rubber.
CN201911113060.3 discloses an ozone resistant rubber sole, which consists of the following raw materials in parts by weight: butadiene rubber, solution polymerized styrene-butadiene rubber, natural rubber, intercalated graphene oxide, white carbon black, rubber powder, liquid polyisobutylene, zinc oxide, petroleum resin, polyethylene glycol, a coupling agent, polyethylene wax, stearic acid, an antioxidant, a vulcanization accelerator DM, insoluble sulfur and a vulcanization accelerator NS; according to the invention, other raw materials except insoluble sulfur and a vulcanization accelerator NS are mixed for reaction, namely, the vulcanization accelerator DM is banburying with the other raw materials, the ozone resistance of a material system can be increased by adopting the adding method, meanwhile, in order to avoid the failure of the accelerator, the compatibility of liquid polyisobutene and petroleum resin adjusting sizing materials is increased in the raw materials, and the reinforcing effect of the material is enhanced by utilizing intercalated graphene oxide, so that the auxiliary agent in the material system is not easy to migrate and aggregate. The art mentions the anti-migration effect of auxiliaries using polyisobutene; however, the relation between polyisobutylene and a fully vulcanized system is not concerned, and the anti-blooming effect of the rubber simply using polyisobutylene is very limited.
CN201510224269.2 discloses a particle type anti-emetic agent pre-dispersed masterbatch for rubber, comprising: 70-80 parts of polyisobutylene, 20-30 parts of filler, 15-20 parts of physical anti-aging agent and 2.5-5 parts of anti-sticking agent; further, the filler is fumed silica, the physical anti-aging agent is fully refined paraffin, and the anti-sticking agent is zinc stearate. The invention also discloses a preparation method of the composition, comprising the following steps: 1) And banburying: adding a physical anti-aging agent, a filler, polyisobutene and an anti-sticking agent in a certain proportion into an internal mixer for mixing, wherein the temperature is 50-65 ℃ and the time is 8-12 min; (2) a granulating step: and after the material mixing is finished, feeding the mixture into a granulator for granulation. However, the masterbatch in the technology has no full vulcanization function, but only uses polyisobutene, and has very limited anti-frosting effect.
CN201710300831.4 relates to the technical field of high molecular materials, and discloses a composite auxiliary agent for producing rubber products, wherein the composite auxiliary agent comprises the following raw materials: the preparation method comprises the steps of adding an active agent, an anti-aging agent, an anti-frosting agent, an adhesive, an accelerator, a dispersing agent, an internal mold release agent and a release agent into an internal mixer, banburying for 20 minutes, and finally extruding and granulating the mixture through a single screw rod, and cooling to obtain the composite additive. The composite auxiliary agent mentioned by the technology does not contain vulcanizing agent, so that the composite auxiliary agent does not have the function of fully vulcanizing components, and meanwhile, the utilization rate of each auxiliary agent is the same as that of each auxiliary agent used independently, and the effect of improving the efficiency of the auxiliary agent is not achieved.
Disclosure of Invention
In order to solve the technical problems, the invention provides the anti-blooming full-vulcanization system dispersion master batch which has anti-blooming capability, and can solve the problems of serious dust of the existing powder auxiliary agent and single function of the existing auxiliary agent master batch.
Therefore, the invention provides a full-vulcanization system dispersion master batch for resisting blooming, which comprises the following steps:
mixing polyisobutylene, a rubber accelerator and sulfur, granulating to obtain primary master batches, and heating and curing the primary master batches to obtain dispersed master batches;
the weight of the polyisobutene is 100 parts, and the weight of each component is as follows: 300-1000 parts of rubber accelerator and 100-2000 parts of sulfur.
Specifically, the dispersed master batch is prepared by blending polyisobutylene with a rubber accelerator and sulfur, granulating the mixture by a granulator to obtain primary master batch, and curing the primary master batch at high temperature to ensure that the rubber accelerator and sulfur can be fully pre-reacted at a higher concentration to form an accelerator-sulfur complex serving as an actual vulcanizing agent, and forming a fully vulcanized system dispersed master batch with an anti-frosting function with the polyisobutylene.
The dosage of the rubber accelerator is preferably 500-900 parts, and the dosage of the sulfur is preferably 200-800 parts.
The polyisobutene is preferably polyisobutene with a number average molecular weight of 20000 or more.
The fully-vulcanized system dispersion master batch disclosed by the invention is characterized in that the accelerator is one or more selected from DM, M, DPG, CZ, TMTD, NS.
The preparation method of the fully vulcanized system dispersion master batch comprises the following steps of: the primary master batch is treated for 1 to 60 minutes at the temperature of 100 to 180 ℃.
Specifically, the heating curing process can be performed in an internal mixer or a screw extruder, i.e. the final discharge temperature of the internal mixer or the screw extruder can be controlled to be the temperature of high-temperature curing.
The preparation method of the fully vulcanized system dispersion master batch disclosed by the invention is characterized in that the heating curing is preferably as follows: the primary master batch is treated for 5-20 minutes at 140-160 ℃.
The fully-vulcanized system dispersion master batch can also contain 20-200 parts of ethylene propylene rubber so as to improve the granulation process performance when a large amount of accelerator and sulfur are used, and the powder is easier to bond during granulation.
The full-vulcanization system dispersion master batch can also contain zinc oxide and stearic acid so as to contain a further optimized vulcanization system on the basis of a complete vulcanization system, and the usage of the master batch for preparing the rubber compound can greatly reduce the usage amount of auxiliary agents.
According to the preparation method of the full-vulcanization system dispersion master batch, the blending is achieved by adopting a blending device commonly used in industry, wherein the blending is preferably performed by adopting a single-twin-screw extruder, an internal mixer or an open mill.
According to the preparation method of the full-vulcanization system dispersion master batch, the granulation adopts an extrusion granulator commonly used in industry, namely a general machine capable of extruding and cutting the mixture into granules; among them, it is preferable that the granulation is performed by an extrusion granulator.
The invention has the following beneficial effects:
(1) In the dispersed master batch prepared by the invention, the polyisobutene can play a role of an adhesive on one hand, so that the master batch has better adhesive strength, is not easy to break and pulverize in the transportation and packaging processes, can form a denser network structure in use, and has higher anti-frosting performance.
(2) In the dispersion master batch prepared by the invention, the rubber accelerator and the sulfur are fully mixed in the primary master batch, and the concentration is much higher than that of the rubber accelerator and the sulfur in the primary master batch when the rubber accelerator and the sulfur are mixed in the traditional rubber, so that the rubber accelerator and the sulfur can fully react in advance to complete the first-step reaction of vulcanization when the rubber accelerator and the sulfur are cured at high temperature, a large amount of accelerator-sulfur complex is generated, the sulfur and the accelerator are consumed in advance, the concentration of sulfur and the accelerator of a system when the rubber accelerator and the sulfur accelerator are used for the rubber is reduced, the vulcanization degree is improved, the free sulfur and the accelerator are lower in content, the residual sulfur-accelerator complex is more difficult to migrate under the network structure of polyisobutene, and the sulfur and the accelerator are synergistic, so that the possibility of frosting is further avoided.
(3) In the master batch prepared by the invention, the accelerator-vulcanization complex is generated by reaction under high concentration in advance, so that the master batch has extremely high reaction efficiency compared with the traditional accelerator-vulcanization complex generated by reaction under low concentration in a rubber system, and the consumption of sulfur and accelerator in the vulcanization process can be greatly reduced.
(4) In the dispersion master batch prepared by the invention, the polyisobutene is used as an adhesive at the same time, so that a large amount of powdery accelerator and sulfur can be adhered, and granulation can be realized. Meanwhile, the polyisobutene is in a saturated structure and cannot be vulcanized by sulfur, so that the polyisobutene cannot be crosslinked in the subsequent high-temperature curing process.
Detailed Description
The following describes embodiments of the present invention in detail: the present example is implemented on the premise of the technical scheme of the present invention, and detailed implementation modes and processes are given, but the protection scope of the present invention is not limited to the following examples, and experimental methods without specific conditions are not noted in the following examples, and generally according to conventional conditions.
Example 1
The formulation is shown in the following table (unit PHR, parts added per 100 parts by mass of rubber (or resin):
TABLE 1
The preparation process comprises the following steps: the polyisobutene, zinc oxide and stearic acid in the formula are put into an internal mixer for preliminary banburying, the accelerator and sulfur are put into the internal mixer for full mixing after about 1 minute, the internal mixer is controlled to be at a temperature not higher than 100 ℃ for discharging, then the mixed master batch is put into an extrusion granulator for granulation, and the prepared master batch is placed for 2 hours and then is put into a temperature of 140 ℃ for curing for 20 minutes, so that the master batch of the product is obtained.
Comparative examples 1 to 1
The formulation is shown in the following table (unit PHR, parts added per 100 parts by mass of rubber (or resin):
TABLE 2
| Polyisobutene (molecular weight 40000) | 100 |
| Accelerator DM | 250 |
| Accelerator M | 200 |
| Accelerator D | 50 |
| Sulfur yellow | 200 |
| Zinc oxide | 250 |
| Stearic acid | 50 |
The preparation process comprises the following steps: and (3) adding the polyisobutene, the zinc oxide and the stearic acid in the formula into an internal mixer for preliminary banburying, adding the accelerator and the sulfur after about 1 minute, fully mixing, controlling the temperature of the internal mixer to be not more than 100 ℃, discharging, adding the mixed master batch into an extrusion granulator for granulating, and standing the prepared master batch for 2 hours to obtain the product master batch.
Comparative examples 1 to 2
The formulation is shown in the following table (unit PHR, parts added per 100 parts by mass of rubber (or resin):
TABLE 3 Table 3
| Nitrile rubber | 100 |
| Accelerator DM | 250 |
| Accelerator M | 200 |
| Accelerator D | 50 |
| Sulfur yellow | 200 |
| Zinc oxide | 250 |
| Stearic acid | 50 |
The preparation process comprises the following steps: putting nitrile rubber, zinc oxide and stearic acid in a formula into an internal mixer for preliminary banburying, putting an accelerator and sulfur after about 1 minute, fully mixing, controlling the temperature of the internal mixer to be not higher than 100 ℃, discharging, putting the mixed master batch into an extrusion granulator for granulation, standing the prepared master batch for 2 hours, and then putting the master batch into the temperature of 140 ℃ for curing for 20 minutes to obtain the product master batch.
Comparative examples 1 to 3
The formulation of example 1 was not granulated and was simply mixed to give the product.
The vulcanization speed analysis method comprises the following steps: according to the following formula, mixing the products of the examples or the comparative examples according to a GB/T6308-2006 open mill method, using a rotor-free vulcanizing machine after mixing, and analyzing at 160 ℃ for 30min according to a GB/T16584-1996 method to obtain the positive vulcanizing time.
The formulation is shown in the following table (unit PHR, supra):
TABLE 4 Table 4
| Nitrile rubber, acrylonitrile content 33%, mooney55 | 100 |
| 8# Standard carbon black | 40 |
| Example 1 and comparative example product or masterbatch | 2 |
The method for testing the amount of the master batch required by 20min positive vulcanization comprises the following steps: mixing the products of the examples or the comparative examples according to a GB/T6308-2006 open mill method, and analyzing to obtain the positive vulcanization time by using a rotor-free vulcanizing instrument according to a GB/T16584-1996 method at 160 ℃ under the condition of 30 min. And adjusting the product dosage of the example 1 and the comparative example to obtain the product dosage when the positive vulcanization time is 20 min.
The formulation is shown in the following table (unit PHR, supra):
TABLE 5
| Nitrile rubber, acrylonitrile content 33%, mooney 55 | 100 |
| 8# Standard carbon black | 40 |
| Example 1 and comparative example product or masterbatch | Adjusting and determining |
The anti-blooming performance test method comprises the following steps: mixing the products of the examples or the comparative examples according to the method of an open mill of GB/T6308-2006, standing for 48 hours at normal temperature, and checking whether the surface has frosting.
The formulations used are shown in the following table (unit PHR, supra):
TABLE 6
| Nitrile rubber, acrylonitrile content 33%, mooney 55 | 100 |
| 8# Standard carbon black | 40 |
| Example 1 and comparative example product or masterbatch | 5 |
Examples and comparative examples the test results are shown in tables 30 to 32.
Example 2
The formulation is shown in the following table (unit PHR, supra):
TABLE 7
The operation process comprises the following steps: the polyisobutene, zinc oxide and stearic acid in the formula are put into an internal mixer for preliminary banburying, the accelerator and sulfur are put into the internal mixer for full mixing after about 1 minute, the internal mixer is controlled to be at a temperature not higher than 100 ℃ for discharging, then the mixed master batch is put into an extrusion granulator for granulation, and the prepared master batch is placed for 2 hours and then is put into a temperature of 180 ℃ for curing for 5 minutes, so that the master batch of the product is obtained.
Comparative example 2-1
The formulation is shown in the following table (unit PHR, supra):
TABLE 8
| Polyisobutene (molecular weight 80000) | 100 |
| Accelerator DM | 250 |
| Accelerator M | 200 |
| Accelerator D | 50 |
| Sulfur yellow | 800 |
| Zinc oxide | 250 |
| Stearic acid | 50 |
The operation process comprises the following steps: and (3) adding the polyisobutene, the zinc oxide and the stearic acid in the formula into an internal mixer for preliminary banburying, adding the accelerator and the sulfur after about 1 minute, fully mixing, controlling the temperature of the internal mixer to be not more than 100 ℃, discharging, adding the mixed master batch into an extrusion granulator for granulating, and standing the prepared master batch for 2 hours to obtain the product master batch.
Comparative examples 2 to 2
The formulation is shown in the following table (unit PHR, supra):
TABLE 9
| Styrene butadiene rubber 1500 | 100 |
| Accelerator DM | 250 |
| Accelerator M | 200 |
| Accelerator D | 50 |
| Sulfur yellow | 800 |
| Zinc oxide | 250 |
| Stearic acid | 50 |
The operation process comprises the following steps: adding styrene-butadiene rubber, zinc oxide and stearic acid in the formula into an internal mixer for preliminary banburying, adding an accelerator and sulfur after about 1 minute, fully mixing, controlling the temperature of the internal mixer to be not higher than 100 ℃, discharging, adding the mixed master batch into an extrusion granulator for granulation, standing the prepared master batch for 2 hours, and then adding the master batch into the temperature of 180 ℃ for curing for 5 minutes to obtain the product master batch.
Comparative examples 2 to 3
The formulation of example 2 was not granulated and was simply mixed to give the product.
The vulcanization speed analysis method comprises the following steps: according to the following formula, mixing the products of the examples or the comparative examples according to a GB/T6308-2006 open mill method, using a rotor-free vulcanizing machine after mixing, and analyzing at 160 ℃ for 30min according to a GB/T16584-1996 method to obtain the positive vulcanizing time.
The formulation is shown in the following table (unit PHR, supra):
table 10
| Nitrile rubber, acrylonitrile content 33%, mooney 55 | 100 |
| 8# Standard carbon black | 40 |
| Example 2 and comparative example product or masterbatch | 2 |
The method for testing the amount of the master batch required by 20min positive vulcanization comprises the following steps: mixing the products of the examples or the comparative examples according to a GB/T6308-2006 open mill method, and analyzing to obtain the positive vulcanization time by using a rotor-free vulcanizing instrument according to a GB/T16584-1996 method at 160 ℃ under the condition of 30 min. And adjusting the product dosage of the example 2 and the comparative example to obtain the product dosage when the positive vulcanization time is 20 min.
The formulation is shown in the following table (unit PHR, supra):
TABLE 11
| Nitrile rubber, acrylonitrile content 33%, mooney 55 | 100 |
| 8# Standard carbon black | 40 |
| Example 2 and comparative example product or masterbatch | Adjusting and determining |
The anti-blooming performance test method comprises the following steps: mixing the products of the examples or the comparative examples according to the method of an open mill of GB/T6308-2006, standing for 48 hours at normal temperature, and checking whether the surface has frosting.
The formulations used are shown in the following table (unit PHR, supra):
table 12
| Nitrile rubber, acrylonitrile content 33%, mooney 55 | 100 |
| 8# Standard carbon black | 40 |
| Example 2 and comparative example product or masterbatch | 6 |
Examples and comparative examples the test results are shown in tables 30 to 32.
Example 3
The formulation is shown in the following table (unit PHR, supra):
TABLE 13
| Polyisobutene (molecular weight 40000) | 100 |
| Accelerator DM | 150 |
| Accelerator M | 100 |
| Accelerator D | 50 |
| Sulfur yellow | 800 |
| Zinc oxide | 150 |
| Stearic acid | 50 |
The operation process comprises the following steps: the polyisobutene, zinc oxide and stearic acid in the formula are put into an internal mixer for preliminary banburying, the accelerator and sulfur are put into the internal mixer for full mixing after about 1 minute, the internal mixer is controlled to be at a temperature not higher than 100 ℃ for discharging, then the mixed master batch is put into an extrusion granulator for granulation, and the prepared master batch is placed for 2 hours and then is put into 160 ℃ for curing for 10 minutes, so that the master batch of the product is obtained.
Comparative example 3-1
The formulation is shown in the following table (unit PHR, supra):
TABLE 14
| Polyisobutene (molecular weight 40000) | 100 |
| Accelerator DM | 150 |
| Accelerator M | 100 |
| Accelerator D | 50 |
| Sulfur yellow | 800 |
| Zinc oxide | 150 |
| Stearic acid | 50 |
The operation process comprises the following steps: and (3) adding the polyisobutene, the zinc oxide and the stearic acid in the formula into an internal mixer for preliminary banburying, adding the accelerator and the sulfur after about 1 minute, fully mixing, controlling the temperature of the internal mixer to be not more than 100 ℃, discharging, adding the mixed master batch into an extrusion granulator for granulating, and standing the prepared master batch for 2 hours to obtain the product master batch.
Comparative example 3-2
The formulation is shown in the following table (unit PHR, supra):
TABLE 15
The operation process comprises the following steps: putting nitrile rubber, zinc oxide and stearic acid in a formula into an internal mixer for preliminary banburying, putting an accelerator and sulfur after about 1 minute, fully mixing, controlling the temperature of the internal mixer to be not higher than 100 ℃, discharging, putting the mixed master batch into an extrusion granulator for granulation, standing the prepared master batch for 2 hours, and then putting the master batch into 160 ℃ for curing for 10 minutes to obtain the product master batch.
Comparative examples 3 to 3
The formulation of example 3 was not granulated and was simply mixed to give the product.
The vulcanization speed analysis method comprises the following steps: according to the following formula, mixing the products of the examples or the comparative examples according to a GB/T6308-2006 open mill method, using a rotor-free vulcanizing machine after mixing, and analyzing at 160 ℃ for 30min according to a GB/T16584-1996 method to obtain the positive vulcanizing time.
The formulation is shown in the following table (unit PHR, supra):
table 16
| Nitrile rubber, acrylonitrile content 33%, mooney 55 | 100 |
| 8# Standard carbon black | 40 |
| Example 3 and comparative example product or masterbatch | 2 |
The method for testing the amount of the master batch required by 20min positive vulcanization comprises the following steps: mixing the products of the examples or the comparative examples according to a GB/T6308-2006 open mill method, and analyzing to obtain the positive vulcanization time by using a rotor-free vulcanizing instrument according to a GB/T16584-1996 method at 160 ℃ under the condition of 30 min. And adjusting the product dosage of the example 3 and the comparative example to obtain the product dosage when the positive vulcanization time is 20 min.
The formulation is shown in the following table (unit PHR, supra):
TABLE 17
| Nitrile rubber, acrylonitrile content 33%, mooney 55 | 100 |
| 8# Standard carbon black | 40 |
| Example 3 and comparative example product or masterbatch | Adjusting and determining |
The anti-blooming performance test method comprises the following steps: mixing the products of the examples or the comparative examples according to the method of an open mill of GB/T6308-2006, standing for 48 hours at normal temperature, and checking whether the surface has frosting. The formulations used are shown in the following table (unit: PHR):
TABLE 18
| Nitrile rubber, acrylonitrile content 33%, mooney 55 | 100 |
| 8# Standard carbon black | 40 |
| Example 3 and comparative example product or masterbatch | 3 |
Examples and comparative examples the test results are shown in tables 30 to 32.
Example 4
The formulation is shown in the following table (unit: PHR):
TABLE 19
| Polyisobutene (molecular weight 120000) | 100 |
| Accelerator DM | 150 |
| Accelerator M | 100 |
| Promoter CZ | 50 |
| Sulfur yellow | 600 |
| Zinc oxide | 150 |
| Stearic acid | 50 |
| Ethylene propylene diene monomer | 30 |
The operation process comprises the following steps: the polyisobutene, zinc oxide and stearic acid in the formula are put into an internal mixer for preliminary banburying, the accelerator and sulfur are put into the internal mixer for full mixing after about 1 minute, the temperature of the internal mixer is controlled to be not higher than 100 ℃, then the mixture is discharged, then the mixed master batch is put into an extrusion granulator for granulation, and the prepared master batch is placed for 2 hours and then is put into the temperature of 150 ℃ for curing for 15 minutes, thus obtaining the master batch of the product.
Comparative example 4-1
The formulation is shown in the following table (unit: PHR):
table 20
| Polyisobutene (molecular weight 40000) | 100 |
| Accelerator DM | 150 |
| Accelerator M | 100 |
| Accelerator D | 50 |
| Sulfur yellow | 600 |
| Zinc oxide | 150 |
| Stearic acid | 50 |
| Ethylene propylene diene monomer | 30 |
The operation process comprises the following steps: and (3) adding the polyisobutene, the zinc oxide and the stearic acid in the formula into an internal mixer for preliminary banburying, adding the accelerator and the sulfur after about 1 minute, fully mixing, controlling the temperature of the internal mixer to be not higher than 100 ℃, discharging, adding the mixed master batch into an extrusion granulator for granulating, and standing the prepared master batch for 2 hours to obtain the product master batch.
Comparative example 4-2
The formulation is shown in the following table (unit: PHR):
table 21
The operation process comprises the following steps: putting nitrile rubber, zinc oxide and stearic acid in a formula into an internal mixer for preliminary banburying, putting an accelerator and sulfur after about 1 minute, fully mixing, controlling the temperature of the internal mixer to be not higher than 100 ℃, discharging, putting the mixed master batch into an extrusion granulator for granulation, standing the prepared master batch for 2 hours, and then putting the master batch into a temperature of 150 ℃ for curing for 15 minutes to obtain the product master batch.
Comparative examples 4 to 3
The formulation of example 3 was not granulated and was simply mixed to give the product.
The vulcanization speed analysis method comprises the following steps: according to the following formula, mixing the products of the examples or the comparative examples according to a GB/T6308-2006 open mill method, using a rotor-free vulcanizing machine after mixing, and analyzing at 160 ℃ for 30min according to a GB/T16584-1996 method to obtain the positive vulcanizing time.
The formulation is shown in the following table (unit: PHR):
table 22
| Nitrile rubber, acrylonitrile content 33%, mooney 55 | 100 |
| 8# Standard carbon black | 40 |
| Example 4 and comparative product or masterbatch | 2 |
The method for testing the amount of the master batch required by 20min positive vulcanization comprises the following steps: mixing the products of the examples or the comparative examples according to a GB/T6308-2006 open mill method, and analyzing to obtain the positive vulcanization time by using a rotor-free vulcanizing instrument according to a GB/T16584-1996 method at 160 ℃ under the condition of 30 min. And adjusting the product dosage of the example 4 and the comparative example to obtain the product dosage when the positive vulcanization time is 20 min.
The formulation is shown in the following table (unit: PHR):
table 22
| Nitrile rubber, acrylonitrile content 33%, mooney 55 | 100 |
| 8# Standard carbon black | 40 |
| Example 4 and comparative product or masterbatch | Adjusting and determining |
The anti-blooming performance test method comprises the following steps: mixing the products of the examples or the comparative examples according to the method of an open mill of GB/T6308-2006, standing for 48 hours at normal temperature, and checking whether the surface has frosting. The formulations used are shown in the following table (unit: PHR):
table 23
| Nitrile rubber, acrylonitrile content 33%, mooney 55 | 100 |
| 8# Standard carbon black | 40 |
| Example 4 and comparative product or masterbatch | 4 |
Examples and comparative examples the test results are shown in tables 30 to 32.
Example 5
The formulation is shown in the following table (unit: PHR):
table 24
| Polyisobutene (molecular weight 40000) | 100 |
| Accelerator DM | 250 |
| Accelerator M | 200 |
| Accelerator D | 50 |
| Sulfur yellow | 200 |
The operation process comprises the following steps: the polyisobutene in the formula is put into an internal mixer for preliminary banburying, the accelerant and sulfur are put into the internal mixer for full mixing after about 1 minute, the temperature of the internal mixer is controlled to be not higher than 100 ℃, then the internal mixer is discharged, the mixed master batch is put into an extrusion granulator for granulation, and the prepared master batch is placed for 2 hours and then is put into the temperature of 150 ℃ for curing for 20 minutes, so that the product master batch is obtained.
Comparative example 5-1
The formulation is shown in the following table (unit: PHR):
table 25
| Polyisobutene (molecular weight 40000) | 100 |
| Accelerator DM | 250 |
| Accelerator M | 200 |
| Accelerator D | 50 |
| Sulfur yellow | 200 |
The operation process comprises the following steps: and (3) putting the polyisobutene in the formula into an internal mixer for preliminary banburying, putting the accelerator and sulfur after about 1 minute, fully mixing, controlling the temperature of the internal mixer to be not more than 100 ℃, discharging, putting the mixed master batch into an extrusion granulator for granulation, and standing the prepared master batch for 2 hours to obtain the product master batch.
Comparative example 5-2
The formulation is shown in the following table (unit: PHR):
table 26
| Nitrile rubber | 100 |
| Accelerator DM | 250 |
| Accelerator M | 200 |
| Accelerator D | 50 |
| Sulfur yellow | 200 |
The operation process comprises the following steps: and (3) primarily banburying nitrile rubber in the formula in an internal mixer, adding an accelerator and sulfur after about 1 minute, fully mixing, controlling the temperature of the internal mixer to be not higher than 100 ℃, discharging, adding the mixed master batch into an extrusion granulator for granulation, standing the prepared master batch for 2 hours, and then curing at the temperature of 150 ℃ for 20 minutes to obtain the product master batch.
Comparative examples 5 to 3
The formulation of example 5 was not granulated and was simply mixed to give the product.
The vulcanization speed analysis method comprises the following steps: according to the following formula, the products of the examples or the comparative examples are mixed according to the method of a GB/T6308-2006 open mill, after mixing, a rotor-free vulcanizing machine is used, and the positive vulcanizing time is obtained by analysis according to the method of GB/T16584-1996 under the conditions of 160 ℃ and 30 min.
The formulation is shown in the following table (unit: PHR):
table 27
| Nitrile rubber, acrylonitrile content 33%, mooney 55 | 100 |
| 8# Standard carbon black | 40 |
| Zinc oxide | 3 |
| Stearic acid | 1 |
| Example 5 and comparative example product or masterbatch | 2 |
The method for testing the amount of the master batch required by 20min positive vulcanization comprises the following steps: mixing the products of the examples or the comparative examples according to a GB/T6308-2006 open mill method, and analyzing to obtain the positive vulcanization time by using a rotor-free vulcanizing instrument according to a GB/T16584-1996 method at 160 ℃ under the condition of 30 min. And adjusting the product dosage of the example 5 and the comparative example to obtain the product dosage when the positive vulcanization time is 20 min.
The formulation is shown in the following table (unit: PHR):
table 28
| Nitrile rubber, acrylonitrile content 33%, mooney 55 | 100 |
| 8# Standard carbon black | 40 |
| Zinc oxide | 3 |
| Stearic acid | 1 |
| Example 5 and comparative example product or masterbatch | Adjusting and determining |
The anti-blooming performance test method comprises the following steps: mixing the products of the examples or the comparative examples according to the method of an open mill of GB/T6308-2006, standing for 48 hours at normal temperature, and checking whether the surface has frosting. The formulations used are shown in the following table (unit: PHR):
table 29
| Nitrile rubber, acrylonitrile content 33%, mooney 55 | 100 |
| 8# Standard carbon black | 40 |
| Zinc oxide | 3 |
| Stearic acid | 1 |
| Example 1 and comparative example product or masterbatch | 5 |
Examples and comparative examples the test results are shown in tables 30 to 32.
Performance comparison results:
positive cure time results (rounded to min after decimal):
table 30
It can be seen from the vulcanization rate that the vulcanization rate can be significantly improved by using the method of the present invention, as compared with the comparative example.
Product usage results (phr) for 20min forward vulcanization:
table 31
| Example 1 | 0.5 |
| Comparative examples 1 to 1 | 0.8 |
| Comparative examples 1 to 2 | 1 |
| Comparative examples 1 to 3 | 0.7 |
| Example 2 | 0.6 |
| Comparative example 2-1 | 0.9 |
| Comparative examples 2 to 2 | 1.1 |
| Comparative examples 2 to 3 | 1 |
| Example 3 | 0.8 |
| Comparative example 3-1 | 1.1 |
| Comparative example 3-2 | 1.3 |
| Comparative examples 3 to 3 | 1.2 |
| Example 4 | 1.7 |
| Comparative example 4-1 | 2.5 |
| Comparative example 4-2 | 2.9 |
| Comparative examples 4 to 3 | 2.4 |
| Example 5 | 0.5 |
| Comparative example 5-1 | 0.7 |
| Comparative example 5-2 | 0.9 |
| Comparative examples 5 to 3 | 0.9 |
From the viewpoint of the amount of product required for the 20min positive vulcanization time, the masterbatch product prepared by the method of the invention has much lower usage amount of vulcanization aid than the comparative example when the same vulcanization effect is achieved.
Anti-blooming performance contrast:
table 32
| Sample of | Whether to spray or not |
| Example 1 | Whether or not |
| Comparative examples 1 to 1 | Slight |
| Comparative examples 1 to 2 | Is that |
| Comparative examples 1 to 3 | Is that |
| Example 2 | Whether or not |
| Comparative example 2-1 | Slight |
| Comparative examples 2 to 2 | Is that |
| Comparative examples 2 to 3 | Is that |
| Example 3 | Whether or not |
| Comparative example 3-1 | Is that |
| Comparative example 3-2 | Is that |
| Comparative examples 3 to 3 | Is that |
| Example 4 | Whether or not |
| Comparative example 4-1 | Is that |
| Comparative example 4-2 | Is that |
| Comparative examples 4 to 3 | Is that |
| Example 5 | Whether or not |
| Comparative example 5-1 | Slight |
| Comparative example 5-2 | Is that |
| Comparative examples 5 to 3 | Is that |
From the aspect of anti-blooming effect, the scheme provided by the invention has excellent anti-blooming effect.
From the aspect of the overall implementation effect, the full-vulcanization system dispersion master batch with the anti-blooming function prepared by the method has the characteristics of high vulcanization speed, less consumption of vulcanization auxiliary agent and good anti-blooming effect.
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention by one skilled in the art without departing from the spirit and scope of the invention.
Claims (9)
1. The anti-blooming full-vulcanization system dispersion master batch is characterized by comprising the following raw material components in parts by weight:
100 parts of polyisobutene,
300-1000 parts of a rubber accelerator,
100-2000 parts of sulfur.
2. The dispersion master batch according to claim 1, wherein the rubber accelerator is used in an amount of 500 to 900 parts and the sulfur is used in an amount of 200 to 800 parts.
3. The dispersion master batch according to claim 1, wherein the polyisobutylene has a number average molecular weight of 20000 or more.
4. The dispersion master batch according to claim 1, wherein the accelerator is selected from one or more of DM, M, DPG, CZ, TMTD, NS.
5. The dispersion master batch according to claim 1, wherein the preparation method of the dispersion master batch comprises the following steps: (1) Mixing polyisobutylene, a rubber accelerator and sulfur, and granulating to obtain primary master batches; and (2) heating and curing the primary master batch to obtain the dispersed master batch.
6. The dispersion master batch according to claim 5, wherein the heating is done as: the primary master batch is treated for 1 to 60 minutes at the temperature of 100 to 180 ℃.
7. The dispersion master batch according to claim 5, wherein the heating is done as: the primary master batch is treated for 5-20 minutes at 140-160 ℃.
8. The dispersion master batch according to claim 1, wherein the dispersion master batch further comprises 20-200 parts ethylene propylene rubber.
9. The dispersion master batch according to claim 1, wherein the dispersion master batch further comprises 50-2000 parts of zinc oxide and 10-1000 parts of stearic acid.
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