Anti-spray full vulcanization system dispersion master batch

Abstract

The application provides an anti-bloom full-vulcanization system dispersion master batch, which comprises the following raw material components in parts by weight: polyisobutylene 100 parts, rubber accelerator 300-1000 parts, and sulfur 100-2000 parts; the dispersion master batch is prepared by the following method: blending the polyisobutylene, the rubber accelerator and the sulfur, then granulating to obtain primary master batch, and then heating and curing the primary master batch to obtain the dispersion master batch. The full-vulcanization system dispersion master batch has the anti-bloom ability, and can solve the problems of serious dust of existing powder additives and single function of existing additive master batches.

Description

Technical Field

[0001] This invention relates to the field of fully vulcanized system dispersion masterbatch, and more specifically to a fully vulcanized system dispersion masterbatch resistant to blooming. Background Technology

[0002] CN201810961109.X discloses a rubber compounding additive granule, comprising the following components in parts by weight: 20-30 parts rubber, 5-8 parts zinc oxide, 3-5 parts stearic acid, 4-6 parts antioxidant, 0.5-1 part anti-scorching agent, 3-5 parts accelerator, and 2-4 parts vulcanizing agent. The granules are cylindrical with a diameter of 2-5 mm and a height of 5-10 mm. This invention provides rubber compounding additive granules that combine the functions of activator, antioxidant, accelerator, vulcanizing agent, and anti-scorching agent. A small amount of additives can achieve the same effect as traditional production processes. Furthermore, because these multifunctional rubber compounding additive granules are granular masterbatch particles, they effectively improve the dispersion of various rubber additives in rubber, facilitate batching, reduce weighing errors, reduce dust pollution during production, and are beneficial to the health of operators. However, this method only involves a simple combination and mixing of additives, resulting in a high rubber content and a low effective additive content.

[0003] CN201611139624.7 discloses a multifunctional fluororubber expanding agent granules and its preparation method. The components of this multifunctional fluororubber expanding agent include: fluororubber, foaming agent, foam stabilizer, vulcanizing agent, acid absorber, reinforcing agent, anti-scorching agent, and release agent. The preparation method is simple and easy to operate, including steps such as crushing and mixing, compounding and tableting, extrusion granulation, and microwave expanding. The prepared multifunctional fluororubber expanding agent does not clump at room temperature, is easy to mix and compound, has good dispersibility, reduces mixing time, produces no dust, and will not cause skin allergies to operators. It also has high raw material utilization. After compounding, it disperses evenly in rubber products, ensuring the production efficiency and quality of rubber products, which is of great significance to the sustainable development of the rubber manufacturing industry. However, this method does not address the full vulcanization system, vulcanization system pretreatment, and the anti-blooming function of the rubber.

[0004] CN201911113060.3 discloses an ozone-resistant rubber shoe sole, composed of the following raw materials in the following weight parts: cis-butadiene rubber, solution-polymerized styrene-butadiene rubber, natural rubber, intercalated graphene oxide, silica, rubber powder, liquid polyisobutylene, zinc oxide, petroleum resin, polyethylene glycol, coupling agent, polyethylene wax, stearic acid, antioxidant, vulcanization accelerator DM, insoluble sulfur, and vulcanization accelerator NS. This invention increases the ozone resistance of the material system by mixing and reacting the raw materials except for insoluble sulfur and vulcanization accelerator NS, i.e., by mixing the vulcanization accelerator DM with other raw materials. This addition method increases the ozone resistance of the material system. Simultaneously, to avoid accelerator deactivation, liquid polyisobutylene and petroleum resin are added to the raw materials to adjust the compatibility of the rubber compound, and intercalated graphene oxide is used to enhance the reinforcing effect of the material, making it less prone to migration and aggregation of additives in the material system. The technology mentions the anti-additive migration effect of polyisobutylene; however, it does not focus on the relationship between polyisobutylene and the full vulcanization system, and the anti-blooming effect of rubber using polyisobutylene alone is very limited.

[0005] CN201510224269.2 discloses a pre-dispersed masterbatch of granular anti-blooming agent for rubber, comprising: 70-80 parts of polyisobutylene, 20-30 parts of filler, 15-20 parts of physical antioxidant, and 2.5-5 parts of anti-sticking agent; further, the filler is fumed silica, the physical antioxidant is fully refined paraffin wax, and the anti-sticking agent is zinc stearate. The invention also discloses a method for preparing the composition, comprising: (1) a mixing step: a certain proportion of physical antioxidant, filler, polyisobutylene and anti-sticking agent are put into a mixing mill for mixing at a temperature of 50-65°C for 8-12 minutes; (2) a granulation step: after the material is mixed, it is fed into a granulator for granulation. However, the masterbatch in this technology does not have a full vulcanization function, and only uses polyisobutylene, so the anti-blooming effect is very limited.

[0006] CN201710300831.4 relates to the field of polymer materials technology and discloses a composite additive for producing rubber products. The composite additive is composed of the following raw materials: activator, antioxidant, anti-blooming agent, binder, accelerator, dispersant, internal mold release agent, and release agent. The above-mentioned components (activator, antioxidant, anti-blooming agent, binder, accelerator, dispersant, internal mold release agent, and release agent) are added to a mixer and mixed for 20 minutes. Finally, the mixture is granulated by single-screw extrusion and cooled to obtain the composite additive. This composite additive does not contain a vulcanizing agent, therefore it does not have the function of a fully vulcanized component, and the utilization rate of each additive is not the same as when used individually, thus it does not improve the efficiency of the additive. Summary of the Invention

[0007] To solve the above-mentioned technical problems, the present invention provides a fully vulcanized dispersion masterbatch with anti-blooming properties. This fully vulcanized dispersion masterbatch also has anti-blooming capabilities, which can solve the problems of serious dust in existing powder additives and the single function of existing additive masterbatches.

[0008] Therefore, the present invention provides a fully vulcanized system dispersion masterbatch with anti-blooming properties, comprising the following steps:

[0009] Polyisobutylene, rubber accelerator and sulfur are blended and then granulated to obtain primary masterbatch. The primary masterbatch is heated and cured to obtain dispersion masterbatch.

[0010] Based on 100 parts by weight of polyisobutylene, the amounts of each component are as follows: 300-1000 parts of rubber accelerator and 100-2000 parts of sulfur.

[0011] Specifically, the dispersion masterbatch is made by blending polyisobutylene with rubber accelerator and sulfur, then granulating it to obtain a primary masterbatch. The primary masterbatch is then cured at high temperature, allowing the rubber accelerator and sulfur to fully pre-react at a high concentration, forming an accelerator-sulfur complex that serves as the actual vulcanizing agent. This complex, together with polyisobutylene, forms a fully vulcanized dispersion masterbatch with anti-blooming function.

[0012] In the fully vulcanized dispersion masterbatch of the present invention, the amount of rubber accelerator is preferably 500-900 parts, and the amount of sulfur is preferably 200-800 parts.

[0013] In the fully vulcanized dispersion masterbatch of the present invention, the polyisobutylene is preferably polyisobutylene with a number average molecular weight of 20,000 or higher.

[0014] The accelerator in the fully vulcanized system dispersion masterbatch of the present invention is selected from one or more of DM, M, DPG, CZ, TMTD, and NS.

[0015] The method for preparing the fully vulcanized system dispersion masterbatch of the present invention includes heating and curing, wherein the primary masterbatch is treated at 100-180℃ for 1-60 minutes.

[0016] Specifically, the heating and curing process can be carried out in a mixer or a screw extruder, meaning that the final discharge temperature of the mixer or screw extruder can be controlled at the temperature of high-temperature curing.

[0017] The method for preparing the fully vulcanized system dispersion masterbatch of the present invention preferably involves heating and curing the primary masterbatch at 140-160℃ for 5-20 minutes.

[0018] The fully vulcanized dispersion masterbatch of the present invention may also contain 20-200 parts of ethylene propylene diene monomer (EPDM) rubber to improve the granulation process performance when using large amounts of accelerator and sulfur, making the powder easier to bind during granulation.

[0019] The full vulcanization system dispersion masterbatch described in this invention may also contain zinc oxide and stearic acid, so as to include a further optimized vulcanization system on the basis of the complete vulcanization system. Using this masterbatch to prepare the compound can significantly reduce the amount of additives used.

[0020] The preparation method of the fully vulcanized system dispersion masterbatch of the present invention uses industrially common blending equipment for the blending process, preferably using a single or twin screw extruder, internal mixer or open mill.

[0021] The method for preparing the fully vulcanized system dispersion masterbatch of the present invention uses an industrially common extrusion granulator for granulation, which is a general-purpose machine that can extrude and cut the mixture into granules; preferably, the granulation uses an extrusion granulator.

[0022] The beneficial effects of this invention are as follows:

[0023] (1) In the dispersion masterbatch prepared by the present invention, the presence of polyisobutylene can act as an adhesive, making the masterbatch have better adhesive strength, less prone to breakage and powdering during transportation and packaging, and can form a denser network structure during use, thus having higher anti-blooming performance.

[0024] (2) In the dispersion masterbatch prepared by the present invention, the rubber accelerator and sulfur are fully mixed in the primary masterbatch and the concentration is much higher than that when they are mixed in traditional rubber. Therefore, during high-temperature curing, sufficient pre-reaction can be carried out, the first step of vulcanization can be completed in advance, and a large amount of accelerator-sulfur complex is generated, so that sulfur and accelerator are consumed in advance, reducing the concentration of sulfur and accelerator in the system when the product of the present invention is used in rubber. At the same time, the degree of vulcanization is improved, and the content of free sulfur and accelerator is lower. The residual sulfur-accelerator complex is more difficult to migrate under the network structure of polyisobutylene. The two work together to further avoid the possibility of blooming.

[0025] (3) In the masterbatch prepared by the present invention, since the accelerator-vulcanization complex is generated in advance at a high concentration, it has a much higher reaction efficiency than the traditional method of generating the accelerator-vulcanization complex at a low concentration in the rubber system, which can greatly reduce the amount of sulfur and accelerator used in the vulcanization process.

[0026] (4) In the dispersion masterbatch prepared by the present invention, polyisobutylene is also used as a binder, which allows a large amount of powdered accelerator and sulfur to be bonded together, thereby achieving granulation. At the same time, since polyisobutylene has a saturated structure, it will not be vulcanized by sulfur, so that polyisobutylene will not crosslink during the subsequent high-temperature curing process. Detailed Implementation

[0027] The following provides a detailed description of the embodiments of the present invention: These embodiments are implemented based on the technical solution of the present invention, and provide detailed implementation methods and processes. However, the scope of protection of the present invention is not limited to the following embodiments. Experimental methods in the following embodiments that do not specify specific conditions are generally performed under conventional conditions.

[0028] Example 1

[0029] The formulation is shown in the table below (unit: PHR, indicating the number of parts added per 100 parts (by weight) of rubber (or resin):

[0030] Table 1

[0031]

[0032]

[0033] Preparation process: Polyisobutylene, zinc oxide and stearic acid in the formula are put into a mixer for initial mixing. After about 1 minute, accelerator and sulfur are added and mixed thoroughly. After the temperature of the mixer is controlled not to exceed 100°C, the mixture is discharged. Then the mixed masterbatch is put into an extrusion granulator for granulation. After the prepared masterbatch is left to stand for 2 hours, it is placed at 140°C for 20 minutes to mature, thus obtaining the product masterbatch of the present invention.

[0034] Comparative Example 1-1

[0035] The formulation is shown in the table below (unit: PHR, indicating the number of parts added per 100 parts (by weight) of rubber (or resin):

[0036] Table 2

[0037] Polyisobutylene (molecular weight 40,000) 100 Accelerator DM 250 Accelerator M 200 Accelerator D 50 Sulfur 200 Zinc oxide 250 stearic acid 50

[0038] Preparation process: Polyisobutylene, zinc oxide and stearic acid in the formula are put into a mixer for initial mixing. After about 1 minute, accelerator and sulfur are added and mixed thoroughly. After the temperature of the mixer is controlled not to exceed 100℃, the mixture is discharged. Then the mixed masterbatch is put into an extrusion granulator for granulation. After the prepared masterbatch is left to stand for 2 hours, the product masterbatch is obtained.

[0039] Comparative Examples 1-2

[0040] The formulation is shown in the table below (unit: PHR, indicating the number of parts added per 100 parts (by weight) of rubber (or resin):

[0041] Table 3

[0042] Nitrile rubber 100 Accelerator DM 250 Accelerator M 200 Accelerator D 50 Sulfur 200 Zinc oxide 250 stearic acid 50

[0043] Preparation process: The nitrile rubber, zinc oxide and stearic acid in the formula are put into the internal mixer for initial mixing. After about 1 minute, the accelerator and sulfur are added and fully mixed. After the temperature of the internal mixer is controlled not to exceed 100℃, the mixture is discharged. Then the mixed masterbatch is put into the extrusion granulator for granulation. After the prepared masterbatch is left to stand for 2 hours, it is placed at 140℃ for 20 minutes to mature, and the product masterbatch is obtained.

[0044] Comparative Examples 1-3

[0045] The product was obtained by simply mixing the formulation according to Example 1 without granulation.

[0046] Vulcanization rate analysis method: According to the following formula, the products of the examples or comparative examples are mixed using the open mill method of GB / T6308-2006. After mixing, the positive vulcanization time is obtained by using a rotorless vulcanizer at 160℃ for 30min according to the method of GB / T16584-1996.

[0047] The formula is shown in the table below (unit: PHR, same as above):

[0048] Table 4

[0049] Nitrile rubber, acrylonitrile content 33%, Mooney 55 100 8# Standard Carbon Black 40 Example 1 and comparative product or masterbatch 2

[0050] Test method for masterbatch dosage required for 20-minute positive vulcanization: The products of the examples or comparative examples were mixed using the open mill method of GB / T6308-2006. After mixing, the positive vulcanization time was obtained by analyzing the product dosage at 160℃ for 30 minutes using a rotorless vulcanizer according to the method of GB / T16584-1996. The dosage of the products of Example 1 and the comparative examples was adjusted to obtain the product dosage required for a positive vulcanization time of 20 minutes.

[0051] The formula is shown in the table below (unit: PHR, same as above):

[0052] Table 5

[0053] Nitrile rubber, acrylonitrile content 33%, Mooney 55 100 8# Standard Carbon Black 40 Example 1 and comparative product or masterbatch Adjust and determine

[0054] Anti-blooming performance test method: Mix the products of the examples or comparative examples according to the open mill method of GB / T 6308-2006, and then let them stand at room temperature for 48 hours to check whether there is blooming on the surface.

[0055] The formulas used are shown in the table below (unit: PHR, same as above):

[0056] Table 6

[0057] Nitrile rubber, acrylonitrile content 33%, Mooney 55 100 8# Standard Carbon Black 40 Example 1 and comparative product or masterbatch 5

[0058] The test results of the examples and comparative examples are shown in Tables 30 to 32.

[0059] Example 2

[0060] The formula is shown in the table below (unit: PHR, same as above):

[0061] Table 7

[0062]

[0063]

[0064] Operation process: Polyisobutylene, zinc oxide and stearic acid in the formula are put into a mixer for initial mixing. After about 1 minute, the accelerator and sulfur are added and fully mixed. After the temperature of the mixer is controlled not to exceed 100°C, the mixture is discharged. Then the mixed masterbatch is put into an extrusion granulator for granulation. After the prepared masterbatch is left to stand for 2 hours, it is placed at 180°C for 5 minutes to mature, thus obtaining the product masterbatch of the present invention.

[0065] Comparative Example 2-1

[0066] The formula is shown in the table below (unit: PHR, same as above):

[0067] Table 8

[0068] Polyisobutylene (molecular weight 80,000) 100 Accelerator DM 250 Accelerator M 200 Accelerator D 50 Sulfur 800 Zinc oxide 250 stearic acid 50

[0069] Operation process: Polyisobutylene, zinc oxide and stearic acid in the formula are put into a mixer for initial mixing. After about 1 minute, the accelerator and sulfur are added and mixed thoroughly. After the temperature of the mixer is controlled not to exceed 100℃, the mixture is discharged. Then the mixed masterbatch is put into an extrusion granulator for granulation. After the prepared masterbatch is left to stand for 2 hours, the product masterbatch is obtained.

[0070] Comparative Example 2-2

[0071] The formula is shown in the table below (unit: PHR, same as above):

[0072] Table 9

[0073] Styrene-butadiene rubber 1500 100 Accelerator DM 250 Accelerator M 200 Accelerator D 50 Sulfur 800 Zinc oxide 250 stearic acid 50

[0074] Operation process: Styrene-butadiene rubber, zinc oxide and stearic acid in the formula are put into a mixer for initial mixing. After about 1 minute, the accelerator and sulfur are added and mixed thoroughly. The temperature of the mixer is controlled not to exceed 100℃. Then the mixture is discharged and fed into an extrusion granulator for granulation. After the prepared masterbatch is left to stand for 2 hours, it is placed at 180℃ for 5 minutes to mature, and the product masterbatch is obtained.

[0075] Comparative Examples 2-3

[0076] The product was obtained by simply mixing the formulation according to Example 2 without granulation.

[0077] Vulcanization rate analysis method: According to the following formula, the products of the examples or comparative examples are mixed using the open mill method of GB / T6308-2006. After mixing, the positive vulcanization time is obtained by using a rotorless vulcanizer at 160℃ for 30min according to the method of GB / T16584-1996.

[0078] The formula is shown in the table below (unit: PHR, same as above):

[0079] Table 10

[0080] Nitrile rubber, acrylonitrile content 33%, Mooney 55 100 8# Standard Carbon Black 40 Example 2 and comparative product or masterbatch 2

[0081] Test method for masterbatch dosage required for 20-minute positive vulcanization: The products of the examples or comparative examples were mixed using the open mill method of GB / T6308-2006. After mixing, the positive vulcanization time was analyzed using a rotorless vulcanizer at 160℃ for 30 minutes according to the method of GB / T16584-1996. The dosage of the products of Example 2 and the comparative examples was adjusted to obtain the product dosage required for a positive vulcanization time of 20 minutes.

[0082] The formula is shown in the table below (unit: PHR, same as above):

[0083] Table 11

[0084] Nitrile rubber, acrylonitrile content 33%, Mooney 55 100 8# Standard Carbon Black 40 Example 2 and comparative product or masterbatch Adjust and determine

[0085] Anti-blooming performance test method: Mix the products of the examples or comparative examples according to the open mill method of GB / T 6308-2006, and then let them stand at room temperature for 48 hours to check whether there is blooming on the surface.

[0086] The formulas used are shown in the table below (unit: PHR, same as above):

[0087] Table 12

[0088] Nitrile rubber, acrylonitrile content 33%, Mooney 55 100 8# Standard Carbon Black 40 Example 2 and comparative product or masterbatch 6

[0089] The test results of the examples and comparative examples are shown in Tables 30 to 32.

[0090] Example 3

[0091] The formula is shown in the table below (unit: PHR, same as above):

[0092] Table 13

[0093] Polyisobutylene (molecular weight 40,000) 100 Accelerator DM 150 Accelerator M 100 Accelerator D 50 Sulfur 800 Zinc oxide 150 stearic acid 50

[0094] Operation process: Polyisobutylene, zinc oxide and stearic acid in the formula are put into a mixer for initial mixing. After about 1 minute, the accelerator and sulfur are added and mixed thoroughly. After the temperature of the mixer is controlled not to exceed 100°C, the mixture is discharged. Then the mixed masterbatch is put into an extrusion granulator for granulation. After the prepared masterbatch is left to stand for 2 hours, it is placed at 160°C for 10 minutes to mature, thus obtaining the product masterbatch of the present invention.

[0095] Comparative Example 3-1

[0096] The formula is shown in the table below (unit: PHR, same as above):

[0097] Table 14

[0098] Polyisobutylene (molecular weight 40,000) 100 Accelerator DM 150 Accelerator M 100 Accelerator D 50 Sulfur 800 Zinc oxide 150 stearic acid 50

[0099] Operation process: Polyisobutylene, zinc oxide and stearic acid in the formula are put into a mixer for initial mixing. After about 1 minute, the accelerator and sulfur are added and mixed thoroughly. After the temperature of the mixer is controlled not to exceed 100℃, the mixture is discharged. Then the mixed masterbatch is put into an extrusion granulator for granulation. After the prepared masterbatch is left to stand for 2 hours, the product masterbatch is obtained.

[0100] Comparative Example 3-2

[0101] The formula is shown in the table below (unit: PHR, same as above):

[0102] Table 15

[0103]

[0104]

[0105] Operation process: The nitrile rubber, zinc oxide and stearic acid in the formula are put into the internal mixer for initial mixing. After about 1 minute, the accelerator and sulfur are added and fully mixed. The temperature of the internal mixer is controlled not to exceed 100℃. Then the mixture is discharged and fed into the extrusion granulator for granulation. After the prepared masterbatch is left to stand for 2 hours, it is placed at 160℃ for 10 minutes to mature, and the product masterbatch is obtained.

[0106] Comparative Example 3-3

[0107] The product was obtained by simply mixing the formulation according to Example 3 without granulation.

[0108] Vulcanization rate analysis method: According to the following formula, the products of the examples or comparative examples are mixed using the open mill method of GB / T6308-2006. After mixing, the positive vulcanization time is obtained by using a rotorless vulcanizer at 160℃ for 30min according to the method of GB / T16584-1996.

[0109] The formula is shown in the table below (unit: PHR, same as above):

[0110] Table 16

[0111] Nitrile rubber, acrylonitrile content 33%, Mooney 55 100 8# Standard Carbon Black 40 Example 3 and comparative product or masterbatch 2

[0112] Test method for masterbatch dosage required for 20-minute positive vulcanization: The products of the examples or comparative examples were mixed using the open mill method of GB / T6308-2006. After mixing, the positive vulcanization time was analyzed using a rotorless vulcanizer at 160℃ for 30 minutes according to the method of GB / T16584-1996. The dosage of the products of Example 3 and the comparative examples was adjusted to obtain the product dosage required for a positive vulcanization time of 20 minutes.

[0113] The formula is shown in the table below (unit: PHR, same as above):

[0114] Table 17

[0115] Nitrile rubber, acrylonitrile content 33%, Mooney 55 100 8# Standard Carbon Black 40 Example 3 and comparative product or masterbatch Adjust and determine

[0116] Anti-blooming performance test method: The products of the examples or comparative examples are mixed according to the open mill method of GB / T 6308-2006, and then left to stand at room temperature for 48 hours. Check whether there is blooming on the surface. The formulas used are shown in the table below (unit: PHR):

[0117] Table 18

[0118] Nitrile rubber, acrylonitrile content 33%, Mooney 55 100 8# Standard Carbon Black 40 Example 3 and comparative product or masterbatch 3

[0119] The test results of the examples and comparative examples are shown in Tables 30 to 32.

[0120] Example 4

[0121] The formula is shown in the table below (unit: PHR):

[0122] Table 19

[0123] Polyisobutylene (molecular weight 120,000) 100 Accelerator DM 150 Accelerator M 100 Accelerator CZ 50 Sulfur 600 Zinc oxide 150 stearic acid 50 ethylene propylene diene monomer (EPDM) rubber 30

[0124] Operation process: Polyisobutylene, zinc oxide and stearic acid in the formula are put into a mixer for initial mixing. After about 1 minute, the accelerator and sulfur are added and mixed thoroughly. The temperature of the mixer is controlled not to exceed 100°C. Then the mixture is discharged and fed into an extrusion granulator for granulation. After the prepared masterbatch is left to stand for 2 hours, it is placed at 150°C for 15 minutes to mature, thus obtaining the product masterbatch of the present invention.

[0125] Comparative Example 4-1

[0126] The formula is shown in the table below (unit: PHR):

[0127] Table 20

[0128] Polyisobutylene (molecular weight 40,000) 100 Accelerator DM 150 Accelerator M 100 Accelerator D 50 Sulfur 600 Zinc oxide 150 stearic acid 50 ethylene propylene diene monomer (EPDM) rubber 30

[0129] Operation process: Polyisobutylene, zinc oxide and stearic acid in the formula are put into a mixer for initial mixing. After about 1 minute, the accelerator and sulfur are added and mixed thoroughly. The temperature of the mixer is controlled not to exceed 100℃. Then the mixture is discharged and fed into an extrusion granulator for granulation. The prepared masterbatch is left to stand for 2 hours to obtain the product masterbatch.

[0130] Comparative Example 4-2

[0131] The formula is shown in the table below (unit: PHR):

[0132] Table 21

[0133]

[0134]

[0135] Operation process: The nitrile rubber, zinc oxide and stearic acid in the formula are put into the internal mixer for initial mixing. After about 1 minute, the accelerator and sulfur are added and mixed thoroughly. The temperature of the internal mixer is controlled not to exceed 100℃. Then the mixture is discharged and fed into the extrusion granulator for granulation. After the prepared masterbatch is left to stand for 2 hours, it is placed at 150℃ for 15 minutes to mature, and the product masterbatch is obtained.

[0136] Comparative Example 4-3

[0137] The product was obtained by simply mixing the formulation according to Example 3 without granulation.

[0138] Vulcanization rate analysis method: According to the following formula, the products of the examples or comparative examples are mixed according to the open mill method of GB / T6308-2006. After mixing, the positive vulcanization time is obtained by using a rotorless vulcanizer at 160℃ for 30min according to the method of GB / T16584-1996.

[0139] The formula is shown in the table below (unit: PHR):

[0140] Table 22

[0141] Nitrile rubber, acrylonitrile content 33%, Mooney 55 100 8# Standard Carbon Black 40 Example 4 and comparative product or masterbatch 2

[0142] Test method for masterbatch dosage required for 20-minute positive vulcanization: The products of the examples or comparative examples were mixed using the open mill method of GB / T6308-2006. After mixing, the positive vulcanization time was obtained by analyzing the product dosage at 160℃ for 30 minutes using a rotorless vulcanizer according to the method of GB / T16584-1996. The dosage of the products of Example 4 and the comparative examples was adjusted to obtain the product dosage required for a positive vulcanization time of 20 minutes.

[0143] The formula is shown in the table below (unit: PHR):

[0144] Table 22

[0145] Nitrile rubber, acrylonitrile content 33%, Mooney 55 100 8# Standard Carbon Black 40 Example 4 and comparative product or masterbatch Adjust and determine

[0146] Anti-blooming performance test method: The products of the examples or comparative examples are mixed according to the open mill method of GB / T 6308-2006, and then left to stand at room temperature for 48 hours. Check whether there is blooming on the surface. The formulas used are shown in the table below (unit: PHR):

[0147] Table 23

[0148] Nitrile rubber, acrylonitrile content 33%, Mooney 55 100 8# Standard Carbon Black 40 Example 4 and comparative product or masterbatch 4

[0149] The test results of the examples and comparative examples are shown in Tables 30 to 32.

[0150] Example 5

[0151] The formula is shown in the table below (unit: PHR):

[0152] Table 24

[0153] Polyisobutylene (molecular weight 40,000) 100 Accelerator DM 250 Accelerator M 200 Accelerator D 50 Sulfur 200

[0154] Operation process: The polyisobutylene in the formula is put into the internal mixer for initial mixing. After about 1 minute, the accelerator and sulfur are added and fully mixed. The temperature of the internal mixer is controlled not to exceed 100°C. Then the mixture is discharged and put into the extrusion granulator for granulation. After the prepared masterbatch is left to stand for 2 hours, it is placed at 150°C for 20 minutes to mature, thus obtaining the product masterbatch of the present invention.

[0155] Comparative Example 5-1

[0156] The formula is shown in the table below (unit: PHR):

[0157] Table 25

[0158] Polyisobutylene (molecular weight 40,000) 100 Accelerator DM 250 Accelerator M 200 Accelerator D 50 Sulfur 200

[0159] Operation process: The polyisobutylene in the formula is put into the internal mixer for initial mixing. After about 1 minute, the accelerator and sulfur are added and fully mixed. After the temperature of the internal mixer is controlled not to exceed 100℃, the mixture is discharged. Then the mixed masterbatch is put into the extrusion granulator for granulation. After the prepared masterbatch is left to stand for 2 hours, the product masterbatch is obtained.

[0160] Comparative Example 5-2

[0161] The formula is shown in the table below (unit: PHR):

[0162] Table 26

[0163] Nitrile rubber 100 Accelerator DM 250 Accelerator M 200 Accelerator D 50 Sulfur 200

[0164] Operation process: The nitrile rubber in the formula is put into the internal mixer for initial mixing. After about 1 minute, the accelerator and sulfur are added and fully mixed. After the temperature of the internal mixer is controlled not to exceed 100℃, the mixture is discharged. Then the mixed masterbatch is put into the extrusion granulator for granulation. After the prepared masterbatch is left to stand for 2 hours, it is placed at 150℃ for 20 minutes to mature, and the product masterbatch is obtained.

[0165] Comparative Example 5-3

[0166] The product was obtained by simply mixing the formulation according to Example 5 without granulation.

[0167] Vulcanization rate analysis method: According to the following formula, the products of the examples or comparative examples are mixed using the open mill method of GB / T6308-2006. After mixing, the positive vulcanization time is obtained by using a rotorless vulcanizer at 160℃ for 30min according to the method of GB / T16584-1996.

[0168] The formula is shown in the table below (unit: PHR):

[0169] Table 27

[0170] Nitrile rubber, acrylonitrile content 33%, Mooney 55 100 8# Standard Carbon Black 40 Zinc oxide 3 stearic acid 1 Example 5 and comparative product or masterbatch 2

[0171] Test method for masterbatch dosage required for 20-minute positive vulcanization: The products of the examples or comparative examples were mixed using the open mill method of GB / T6308-2006. After mixing, the positive vulcanization time was obtained by analyzing the product dosage at 160℃ for 30 minutes using a rotorless vulcanizer according to the method of GB / T16584-1996. The dosage of the products of Example 5 and the comparative examples was adjusted to obtain the product dosage required for a positive vulcanization time of 20 minutes.

[0172] The formula is shown in the table below (unit: PHR):

[0173] Table 28

[0174] Nitrile rubber, acrylonitrile content 33%, Mooney 55 100 8# Standard Carbon Black 40 Zinc oxide 3 stearic acid 1 Example 5 and comparative product or masterbatch Adjust and determine

[0175] Anti-blooming performance test method: The products of the examples or comparative examples are mixed according to the open mill method of GB / T 6308-2006, and then left to stand at room temperature for 48 hours. Check whether there is blooming on the surface. The formulas used are shown in the table below (unit: PHR):

[0176] Table 29

[0177] Nitrile rubber, acrylonitrile content 33%, Mooney 55 100 8# Standard Carbon Black 40 Zinc oxide 3 stearic acid 1 Example 1 and comparative product or masterbatch 5

[0178] The test results of the examples and comparative examples are shown in Tables 30 to 32.

[0179] Performance comparison results:

[0180] Positive vulcanization time results (rounded to the nearest min):

[0181] Table 30

[0182]

[0183]

[0184] As can be seen from the vulcanization rate, the vulcanization rate can be significantly improved by using the implementation method of the present invention compared with the comparative example.

[0185] Product usage results (phr) for 20-minute positive vulcanization:

[0186] Table 31

[0187] Example 1 0.5 Comparative Example 1-1 0.8 Comparative Examples 1-2 1 Comparative Examples 1-3 0.7 Example 2 0.6 Comparative Example 2-1 0.9 Comparative Example 2-2 1.1 Comparative Examples 2-3 1 Example 3 0.8 Comparative Example 3-1 1.1 Comparative Example 3-2 1.3 Comparative Example 3-3 1.2 Example 4 1.7 Comparative Example 4-1 2.5 Comparative Example 4-2 2.9 Comparative Example 4-3 2.4 Example 5 0.5 Comparative Example 5-1 0.7 Comparative Example 5-2 0.9 Comparative Example 5-3 0.9

[0188] Considering the amount of product required for a 20-minute positive vulcanization time, the masterbatch product prepared using the method of this invention requires a significantly lower amount of vulcanization auxiliaries to achieve the same vulcanization effect compared to the comparative example.

[0189] Comparison of anti-blooming performance:

[0190] Table 32

[0191] sample Do you need to spray cream? Example 1 no Comparative Example 1-1 slight Comparative Examples 1-2 yes Comparative Examples 1-3 yes Example 2 no Comparative Example 2-1 slight Comparative Example 2-2 yes Comparative Examples 2-3 yes Example 3 no Comparative Example 3-1 yes Comparative Example 3-2 yes Comparative Example 3-3 yes Example 4 no Comparative Example 4-1 yes Comparative Example 4-2 yes Comparative Example 4-3 yes Example 5 no Comparative Example 5-1 slight Comparative Example 5-2 yes Comparative Example 5-3 yes

[0192] In terms of anti-blooming effect, the solution provided by this invention has excellent anti-blooming effect.

[0193] From the overall implementation effect, the fully vulcanized system dispersion masterbatch with anti-blooming function prepared by the method provided by the present invention has the characteristics of fast vulcanization speed, low amount of vulcanization aid, and good anti-blooming effect.

[0194] Of course, the present invention may have other various embodiments. Without departing from the spirit and essence of the present invention, those skilled in the art can make various corresponding changes and modifications according to the present invention, but these corresponding changes and modifications should all fall within the protection scope of the present invention.

Claims

1. A fully vulcanized dispersion masterbatch with anti-blooming properties, characterized in that, The raw material components include the following parts by weight: 100 parts of polyisobutylene 300-1000 parts of rubber accelerator, Sulfur 100-2000 parts; The preparation method of the dispersion masterbatch includes the following steps: (1) mixing polyisobutylene, rubber accelerator and sulfur, and granulating to obtain primary masterbatch; (2) heating and aging the primary masterbatch to obtain dispersion masterbatch.

2. The dispersion masterbatch according to claim 1, characterized in that, The amount of the rubber accelerator is 500-900 parts, and the amount of sulfur is 200-800 parts.

3. The dispersion masterbatch according to claim 1, characterized in that, The polyisobutylene is polyisobutylene with a number average molecular weight of 20,000 or higher.

4. The dispersion masterbatch according to claim 1, characterized in that, The accelerator is selected from one or more of DM, M, DPG, CZ, TMTD, and NS.

5. The dispersion masterbatch according to claim 1, characterized in that, The heating and curing process involves treating the primary masterbatch at 100-180℃ for 1-60 minutes.

6. The dispersion masterbatch according to claim 1, characterized in that, The heating and curing process involves treating the primary masterbatch at 140-160℃ for 5-20 minutes.

7. The dispersion masterbatch according to claim 1, characterized in that, The dispersion masterbatch also includes 20-200 parts of ethylene propylene diene monomer (EPDM) rubber.

8. The dispersion masterbatch according to claim 1, characterized in that, The dispersion masterbatch also includes 50-2000 parts of zinc oxide and 10-1000 parts of stearic acid.

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