Plasticized full vulcanization system dispersion masterbatch

Abstract

The application relates to a plasticizing full-vulcanization system dispersion master batch and a preparation method thereof, the master batch comprises the following raw material components in parts by weight: 100 parts of polyisobutylene, 10-100 parts of a tertiary butyl-containing peroxide, 100-2000 parts of sulfur, and 300-1000 parts of an accelerator; the dispersion master batch is prepared by the following method: after mixing the polyisobutylene, the tertiary butyl-containing peroxide, the sulfur and the accelerator, primary master batches are obtained through granulation, and then the primary master batches are heated at high temperature for a certain time to obtain the full-vulcanization system dispersion master batch with plasticizing capacity.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of rubber product complexing agent, in particular to a kind of plasticizing full-vulcanization system dispersion master batch. BACKGROUND

[0002] CN201810961109.X provides a kind of rubber compound auxiliary particles, belongs to rubber technical field.It includes the following weight fraction components: rubber 20~30 parts, zinc oxide 5~8 parts, stearic acid 3~5 parts, antioxidant 4~6 parts, anti-scorching agent 0.5~1 parts, accelerator 3~5 parts, vulcanizing agent 2~4 parts, the particle is the cylinder with diameter 2~5mm, height 5~10mm.This application provides rubber compound auxiliary particles with five functions of activator, antioxidant, accelerator, vulcanizing agent and anti-scorching agent, the same effect as traditional production process can be achieved using a small amount of auxiliary agent, at the same time, due to the multifunctional rubber compound auxiliary particles are granular masterbatch, on the one hand, it can effectively improve the dispersion effect of various rubber auxiliaries in rubber, on the other hand, it is convenient to dose, reduces the weighing error, reduces the dust pollution to the environment in production, is beneficial to the health of operating personnel.But the invention is only a simple combination and mixing of auxiliary agent, the rubber content is high, and the effective content of auxiliary agent is low.

[0003] CN201611139624.7 relates to fluorine rubber auxiliary and its preparation technical field, specifically a kind of fluorine rubber multifunctional expansion auxiliary particles and its preparation method, the components of the fluorine rubber multifunctional expansion auxiliary agent include: fluorine rubber, foaming agent, foam stabilizer, vulcanizing agent, acid absorber, reinforcing agent, anti-scorching agent and release agent.The preparation method of the application is simple and easy to operate, including: pulverization, mixing, mixing and pressing, extrusion granulation, microwave expansion and other steps, the fluorine rubber multifunctional expansion auxiliary agent prepared at room temperature does not block, is easy to dose and mix, has good dispersibility, reduces mixing time, does not cause skin allergy phenomenon of operating personnel, raw material utilization rate is high;After dosing and mixing, it is dispersed uniformly in rubber products, which can ensure the production efficiency and quality of rubber products, and has important significance for the sustainable development of rubber manufacturing industry.But, the method does not mention full-vulcanization system, vulcanization system pretreatment and additional plasticizing effect.

[0004] CN201911113060.3 discloses an anti-ozone rubber sole, which is composed of the following components 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, coupling agent, polyethylene wax, stearic acid, antioxidant, vulcanization accelerator DM, insoluble sulfur, vulcanization accelerator NS; the invention mixes and reacts other raw materials except insoluble sulfur and vulcanization accelerator NS, i.e. vulcanization accelerator DM is mixed and kneaded with other raw materials, which can increase the anti-ozone performance of the material system, and in order to avoid the failure of the accelerator, 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, so that the additives in the material system are not easy to migrate and aggregate. The invention mentions the anti-additive migration effect of polyisobutylene, but does not focus on its relationship with the full vulcanization system and the plasticizing effect of the rubber.

[0005] CN202010461428.1 relates to the rubber additive technology field, and discloses an environmentally friendly comprehensive accelerator pre-dispersed masterbatch, a preparation method and application thereof. The masterbatch comprises the following components by weight: 20-40 parts of a polymer carrier; 20-40 parts of a pyrithione salt compound; 10-25 parts of a bicyclic amidine compound; 2-5 parts of an organic acid compound; 10-20 parts of an inorganic filler; 2-10 parts of a plasticizer; and 2-10 parts of a dispersing agent. The invention uses pyrithione salt compounds, bicyclic amidine compounds, and organic acid compounds, which have a synergistic effect, do not produce potential toxic substances such as nitrosamine during the vulcanization process, have the characteristics of long scorch time, fast vulcanization speed, and anti-reversion, can be used to replace existing guanidine accelerators, and do not contain carcinogenic components such as o-toluidine during use, which is safe and environmentally friendly. The invention mentions a plasticizing additive masterbatch, but the method used in the prior art is simply to use existing plasticizers for plasticizing.

[0006] CN111763381A relates to a polyolefin high-concentration plasticizer master batch and its preparation method and application. The preparation raw materials of the plasticizer master batch include foamed polyolefin carrier and plasticizer; the plasticizer is a liquid hydrocarbon with a weight average molecular weight of 500-8000 determined by gel permeation chromatography. The invention uses a self-made foamed polyolefin carrier with a network structure of interconnected pores and high porosity, which can fully absorb the plasticizer, thereby preparing a high-concentration plasticizer master batch with less addition amount in the polymer material, uniform dispersion, without affecting the performance of the polymer material itself, while improving the physical properties of the polymer material, maintaining excellent physical and mechanical properties of the polymer material, and the preparation method is simple, low cost and easy to operate. The method simply mentions the use of plasticizer in the master batch to provide plasticizing effect, and does not focus on the additional plasticizing effect after the degradation of polyisobutylene.

[0007] In summary, although there are technical solutions for preparing rubber plasticizing compound additives in the prior art, they are only simple compounding and combination, but they do not focus on the multiple effects of polyisobutylene, and there is no solution for reducing the molecular weight of polyisobutylene to play a plasticizing role. SUMMARY

[0008] Based on the above, the main purpose of the present application is to provide a plasticizing full-vulcanized system dispersion master batch and its preparation method. The dispersion master batch is mainly used for rubber plasticizing, and can also enhance the anti-bloom function of rubber, and the dispersion master batch is a full-vulcanized system, so that the amount of additives used can be greatly reduced when the dispersion master batch is used for the preparation of rubber.

[0009] In order to achieve the above purpose, the present application provides a plasticizing full-vulcanized system dispersion master batch, which comprises the following raw material components by weight:

[0010] polyisobutylene 100 parts,

[0011] tert-butyl-containing peroxide 10-100 parts, preferably 30-70 parts,

[0012] sulfur 100-2000 parts, preferably 200-800 parts,

[0013] accelerator 300-1000 parts, preferably 300-600 parts;

[0014] The dispersion master batch is prepared by the following method: (1) mixing polyisobutylene, tert-butyl peroxide, sulfur and accelerator, and then granulating to obtain a primary master batch; (2) the primary master batch is heated and cured after standing to obtain a dispersion master batch.

[0015] Specifically, since the polyisobutylene itself has no double bond, it cannot be vulcanized with sulfur, but after being treated with tert-butyl peroxide, the polyisobutylene can be degraded and broken, thereby forming a part of low molecular weight polyisobutylene, which has good compatibility with the rubber itself and excellent fluidity, and has a good plasticizing effect on the rubber, so that the master batch has a good plasticizing effect in addition to the function of the full vulcanization system.

[0016] The dispersion master batch described in the application can also include 20-200 parts of ethylene-propylene rubber. The addition of ethylene-propylene rubber can improve the performance of accelerators and sulfur, so that the powder becomes easier to bond during granulation.

[0017] The dispersion master batch described in the application can also include 50-2000 parts of zinc oxide and 10-1000 parts of stearic acid. The addition of zinc oxide and stearic acid makes the dispersion master batch form a more complete vulcanization system, and the use of the dispersion master batch for the preparation of the rubber compound eliminates the need to add multiple vulcanization system additives, reduces the weighing and batching workload, eliminates dust pollution, and can greatly reduce the amount of additives used.

[0018] The dispersion master batch described in the application has a number average molecular weight of the polyisobutylene of 20,000 or more.

[0019] The dispersion master batch described in the application has a number average molecular weight of the polyisobutylene of 20,000 or more.

[0020] The dispersion master batch described in the application has a number average molecular weight of the polyisobutylene of 20,000 or more.

[0021] In order to achieve the above-mentioned purpose, the application also provides a preparation method of a plasticizing full vulcanization system dispersion master batch, which comprises the following preparation steps:

[0022] (1) mixing polyisobutylene, tert-butyl peroxide, sulfur and accelerators, and then granulating to obtain a primary master batch;

[0023] (2) heating and curing the primary master batch after standing to obtain a dispersion master batch.

[0024] Specifically, the preparation method provided by the application uses a specific ratio of polyisobutylene, tert-butyl peroxide, sulfur and accelerators to obtain a primary master batch. During the heating and curing process, the tert-butyl peroxide causes the polyisobutylene to degrade at high temperature, obtaining a polyisobutylene component with a wide molecular weight distribution, and the remaining tert-butyl peroxide can provide a starting vulcanization point in the rubber.

[0025] The preparation method of the present application, the temperature of the mixing is not more than 100 DEG C.

[0026] The preparation method of the present application, the time of the standing is 0.1-4h.

[0027] The preparation method of the present application, the conditions of the ripening are: temperature 160-190 DEG C, time 5-20 minutes.

[0028] The preparation method of the present application, the granulation adopts the extrusion granulator commonly used in industry, that is, the general machine that can extrude and cut the mixture into granules.

[0029] The present application has the following characteristics:

[0030] (1) The preparation method of the dispersion master batch provided by the present application, because of the existence of tert-butyl peroxide, polyisobutylene can be degraded in high temperature treatment and vulcanization process, thereby forming polyisobutylene component with wide molecular weight distribution, which has significant plasticizing effect when applied in rubber.

[0031] (2) The preparation method of the dispersion master batch provided by the present application can prepare single auxiliary master batch with full vulcanization system, and polyisobutylene plays the role of adhesive in the system, so that the master batch has good formability and is not easy to break during transportation and packaging. Meanwhile, after the treatment by the method of the present application in the presence of peroxide, polyisobutylene also plays the role of plasticizer, so that the master batch has the functions of full vulcanization system and plasticizing.

[0032] (3) The preparation method of the dispersion master batch provided by the present application, because the accelerator-sulfur complex is generated in advance at high concentration, the dispersion master batch has extremely high reaction efficiency compared with the traditional method of generating accelerator-sulfur complex at low concentration in rubber system, and the use amount of sulfur and accelerator can be greatly reduced. DETAILED DESCRIPTION

[0033] The following detailed description of the embodiments of the present application is given on the premise of the technical solutions of the present application, and detailed implementation modes and processes are given, but the protection scope of the present application is not limited to the following embodiments. The experimental methods not specified in the following embodiments are usually carried out according to conventional conditions.

[0034] Example 1

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

[0036] Table 1

[0037] Polyisobutylene (number average molecular weight 40000) 100 parts by mass Dibenzoyl peroxide 30 parts by mass Accelerator DM 250 parts by mass Accelerator M 200 parts by mass Accelerator D 50 parts by mass Sulfur 200 parts by mass Zinc oxide 250 parts by mass Stearic acid 50 parts by mass

[0038] Preparation process: the polyisobutylene, zinc oxide and stearic acid in the formula are put into the internal mixer for preliminary mixing (control the temperature of the internal mixer not more than 100℃), the accelerator, sulfur and di-tert-butyl peroxide are put in after about 1 minute, and then the mixture is mixed sufficiently and discharged. Then the mixed masterbatch is put into the extrusion granulator for granulation. The prepared primary masterbatch is placed for 2h and then aged at a temperature of 160℃ for 20 minutes to obtain the product masterbatch.

[0039] Comparative Example 1-1

[0040] The formula is shown in the following table (unit PHR):

[0041] Table 2

[0042] Polyisobutylene (number average molecular weight 40000) 100 parts by mass Dibenzoyl peroxide 30 parts by mass Accelerator DM 250 parts by mass Accelerator M 200 parts by mass Accelerator D 50 parts by mass Sulfur 200 parts by mass Zinc oxide 250 parts by mass Stearic acid 50 parts by mass

[0043] Preparation process: the polyisobutylene, zinc oxide and stearic acid in the formula are put into the internal mixer for preliminary mixing (control the temperature of the internal mixer not more than 100℃), the accelerator, sulfur and di-tert-butyl peroxide are put in after about 1 minute, and then the mixture is mixed sufficiently and discharged. Then the mixed masterbatch is put into the extrusion granulator for granulation. The prepared primary masterbatch is placed for 2h and then aged at a temperature of 160℃ for 20 minutes to obtain the product masterbatch.

[0044] Comparative Example 1-2

[0045] The formula is shown in the following table (unit PHR):

[0046] Table 3

[0047] Nitrile rubber 100 parts by mass Dibenzoyl peroxide 30 parts by mass Accelerator DM 250 parts by mass Accelerator M 200 parts by mass Accelerator D 50 parts by mass Sulfur 200 parts by mass Zinc oxide 250 parts by mass Stearic acid 50 parts by mass

[0048] Preparation process: the polyisobutylene, zinc oxide and stearic acid in the formula are put into the internal mixer for preliminary mixing (control the temperature of the internal mixer not more than 100℃), the accelerator, sulfur and di-tert-butyl peroxide are put in after about 1 minute, and then the mixture is mixed sufficiently and discharged. Then the mixed masterbatch is put into the extrusion granulator for granulation. The prepared primary masterbatch is placed for 2h and then aged at a temperature of 160℃ for 20 minutes to obtain the product masterbatch.

[0049] Comparative Example 1-3

[0050] The product is obtained by mixing according to the formula of Example 1 without granulation.

[0051] Comparative Example 1-4

[0052] The formula is shown in the following table (unit PHR):

[0053] Table 4

[0054] Polyisobutylene (number average molecular weight 40000) 100 parts by mass Accelerator DM 250 parts by mass Accelerator M 200 parts by mass Accelerator D 50 parts by mass Sulfur 200 parts by mass Zinc oxide 250 parts by mass Stearic acid 50 parts by mass

[0055] Preparation process: the polyisobutylene, zinc oxide and stearic acid in the formula are put into the internal mixer for preliminary mixing (control the temperature of the internal mixer not to exceed 100℃), about 1 minute later, the accelerator and sulfur are put in, and after sufficient mixing, the material is discharged, then the mixed masterbatch is put into the extrusion granulator for granulation, the prepared primary masterbatch is placed for 2h, then it is placed in a temperature of 160℃ for curing for 20 minutes, and finally the product masterbatch is obtained.

[0056] Test Example 1

[0057] (1) Analysis method of vulcanization speed: according to the following Table 5, the product of the example or the comparative example is mixed by the open mill method of GB / T 6308-2006, and then the non-rotor vulcanization instrument is used to analyze the vulcanization time under the condition of 160℃ and 30min according to the method of GB / T16584-1996. At the same time, the Mooney viscosity of the mixed rubber is measured by the Mooney viscometer according to GB / T 1232.1-2016 to represent the plasticizing performance. The test results are shown in Table 33.

[0058] The formula is shown in the following table (unit PHR):

[0059] Table 5

[0060] Nitrile rubber, acrylonitrile content 33%, Mooney 55 100 parts by mass 8# standard carbon black 40 parts by mass Example 1 and comparative product or master batch 2 parts by mass

[0061] (2) Test method of the amount of masterbatch required for 20min vulcanization: according to the following Table 6, the product of the example or the comparative example is mixed by the open mill method of GB / T 6308-2006, and then the non-rotor vulcanization instrument is used to analyze the vulcanization time under the condition of 160℃ and 30min according to the method of GB / T16584-1996. The amount of product when the vulcanization time is 20min is obtained by adjusting the amount of the product of Example 1 and the comparative example. The test results are shown in Table 34.

[0062] The formula is shown in the following table (unit PHR):

[0063] Table 6

[0064] Nitrile rubber, acrylonitrile content 33%, Mooney 55 100 parts by mass 8# standard carbon black 40 parts by mass Example 1 and comparative product or master batch Adjust and determine

[0065] (3) Test method of plasticizing performance: according to the following Table 7, the product of the example or the comparative example is mixed by the open mill method of GB / T 6308-2006, and then it is placed for 48h at room temperature, and the Mooney viscosity of the mixed rubber is measured to represent the plasticizing effect. The test results are shown in Table 35.

[0066] The formula is shown in the following table (unit PHR):

[0067] Table 7

[0068]

[0069]

[0070] Example 2

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

[0072] Table 8

[0073] Polyisobutylene (molecular weight 40000) 100 parts by mass Dibenzoyl peroxide 70 parts by mass Accelerator DM 250 parts by mass Accelerator M 200 parts by mass Accelerator D 50 parts by mass Sulfur 800 parts by mass Zinc oxide 250 parts by mass Stearic acid 50 parts by mass

[0074] Preparation process: Polyisobutylene, zinc oxide and stearic acid in the formula are put into a mixer for preliminary mixing (the temperature of the mixer is controlled not to exceed 100°C). After about 1 minute, accelerator, sulfur and di-tert-butyl peroxide are added and fully mixed before discharge. Then the mixed masterbatch is put into an extrusion granulator for granulation. After the prepared primary masterbatch is left to stand for 2 hours, it is placed at 180°C for 5 minutes to mature, and the product masterbatch of the present invention is obtained.

[0075] Comparative Example 2-1

[0076] The formula is shown in the table below (unit: PHR):

[0077] Table 9

[0078]

[0079]

[0080] Preparation process: Polyisobutylene, zinc oxide and stearic acid in the formula are put into a mixer for initial mixing (the temperature of the mixer is controlled not to exceed 100°C). After about 1 minute, accelerator, sulfur and di-tert-butyl peroxide are added and fully mixed before discharge. Then the mixed masterbatch is put into an extrusion granulator for granulation. The prepared primary masterbatch is left to stand for 2 hours to obtain the product masterbatch.

[0081] Comparative Example 2-2

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

[0083] Table 10

[0084] Styrene-butadiene rubber 1500 100 parts by mass Dibenzoyl peroxide 70 parts by mass Accelerator DM 250 parts by mass Accelerator M 200 parts by mass Accelerator D 50 parts by mass Sulfur 800 parts by mass Zinc oxide 250 parts by mass Stearic acid 50 parts by mass

[0085] Preparation process: Styrene-butadiene rubber, zinc oxide and stearic acid in the formula are put into a mixer for initial mixing (the temperature of the mixer is controlled not to exceed 100℃). After about 1 minute, accelerator, sulfur and di-tert-butyl peroxide are added and fully mixed before discharge. Then the mixed masterbatch is put into an extrusion granulator for granulation. After the prepared primary masterbatch is left to stand for 2 hours, it is placed at 180℃ for 5 minutes to mature, and the product masterbatch is obtained.

[0086] Comparative Example 2-3

[0087] The product was obtained by mixing the ingredients of Example 2 without granulation.

[0088] Comparative Example 2-4

[0089] The formulation is shown in the following table (unit: PHR):

[0090] Table 11

[0091] Polyisobutylene (number average molecular weight 40000) 100 parts by mass Accelerator DM 250 parts by mass Accelerator M 200 parts by mass Accelerator D 50 parts by mass Sulfur 800 parts by mass Zinc oxide 250 parts by mass Stearic acid 50 parts by mass

[0092] Preparation process: the polyisobutylene, zinc oxide and stearic acid in the formulation were put into the internal mixer for preliminary mixing (the temperature of the internal mixer was controlled not to exceed 100°C), and after about 1 minute, the accelerator and sulfur were put in for sufficient mixing, and then the mixed masterbatch was put into the extrusion granulator for granulation. The prepared primary masterbatch was placed at a temperature of 180°C for 5 minutes for curing, and then the product masterbatch of the application was obtained.

[0093] Test Example 2

[0094] (I) Analysis method of vulcanization speed: according to the following Table 12, the products of the examples or comparative examples were mixed by the open mill method of GB / T 6308-2006, and then the non-rotor vulcanizer was used to analyze the vulcanization time under the condition of 160°C and 30 min according to the method of GB / T16584-1996. At the same time, the Mooney viscosity of the mixed rubber was measured by the Mooney viscometer according to GB / T 1232.1-2016 to characterize the plasticizing performance. The test results are shown in Table 33.

[0095] The formulation is shown in the following table (unit: PHR):

[0096] Table 12

[0097] Nitrile rubber, acrylonitrile content 33%, Mooney 55 100 parts by mass 8# standard carbon black 40 parts by mass Example 2 and comparative product or master batch 2 parts by mass

[0098] (II) Test method of the amount of masterbatch required for 20 min vulcanization: according to the following Table 13, the products of the examples or comparative examples were mixed by the open mill method of GB / T 6308-2006, and then the non-rotor vulcanizer was used to analyze the vulcanization time under the condition of 160°C and 30 min according to the method of GB / T16584-1996. The amount of product of the examples 2 and comparative examples was adjusted to obtain the amount of product when the vulcanization time was 20 min. The test results are shown in Table 34.

[0099] The formulation is shown in the following table (unit: PHR):

[0100] Table 13

[0101] Nitrile rubber, acrylonitrile content 33%, Mooney 55 100 parts by mass 8# standard carbon black 40 parts by mass Example 2 and comparative product or master batch Adjust and determine

[0102] (III) Plasticizing performance test method: according to the following Table 14, the product of the example or the comparative example is mixed by the open mill method of GB / T 6308-2006, then is placed for 48 h at room temperature, and the mixed glue Mooney viscosity is tested to serve as a representation of the plasticizing effect. The test results are shown in Table 35.

[0103] The formula is shown in the following table (unit: PHR):

[0104] Table 14

[0105] Nitrile rubber, acrylonitrile content 33%, Mooney 55 100 parts by mass 8# standard carbon black 40 parts by mass Example 2 and comparative product or master batch 6 parts by mass

[0106] Example 3

[0107] The formula is shown in the following table (unit: PHR):

[0108] Table 15

[0109] Polyisobutylene (molecular weight 40000) 100 parts by mass 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane 50 parts by mass Accelerator DM 150 parts by mass Accelerator M 100 parts by mass Accelerator D 50 parts by mass Sulfur 800 parts by mass Zinc oxide 150 parts by mass Stearic acid 50 parts by mass

[0110] Preparation process: the polyisobutylene, zinc oxide and stearic acid in the formula are put into the internal mixer for preliminary mixing (the temperature of the internal mixer is controlled to be not more than 100 DEG C), about 1 minute later, the accelerator, sulfur and 2, 5-dimethyl-2, 5-bis (tert-butyl peroxy hexane) are put in, and after sufficient mixing, the material is discharged, then the mixed masterbatch is put into the extrusion granulator for granulation, the prepared masterbatch is placed for 2 h, then is aged for 10 minutes at a temperature of 160 DEG C, and the product masterbatch is obtained.

[0111] Comparative example 3-1

[0112] The formula is shown in the following table (unit: PHR):

[0113] Table 16

[0114]

[0115] Operation process: the polyisobutylene, zinc oxide and stearic acid in the formula are put into the internal mixer for preliminary mixing, about 1 minute later, the accelerator, sulfur and 2, 5-dimethyl-2, 5-bis (tert-butyl peroxy hexane) are put in, and after sufficient mixing, the temperature of the internal mixer is controlled to be not more than 100 DEG C, then the material is discharged, then the mixed masterbatch is put into the extrusion granulator for granulation, the prepared masterbatch is placed for 2 h, and the product masterbatch is obtained.

[0116] Comparative example 3-2

[0117] The formula is shown in the following table (unit: PHR):

[0118] Table 17

[0119]

[0120] Process: Put polyisobutylene, zinc oxide and stearic acid in the formula into the internal mixer for preliminary mixing, after about 1 minute, put the accelerator, sulfur and 2,5-dimethyl-2,5-bis(tert-butyl peroxy) hexane, and mix thoroughly, control the temperature of the internal mixer not to exceed 100℃, then discharge, then put the mixed masterbatch into the extrusion granulator for granulation, and then put the prepared masterbatch into the temperature of 160℃ for 10 minutes, and then the product masterbatch is obtained.

[0121] Comparative Example 3-3

[0122] According to the formula of Example 3, the product is obtained by simply mixing without granulation.

[0123] Test Example 3

[0124] (I) Analysis method of vulcanization speed: according to the following Table 18 formula, the product of the example or the comparative example is mixed by GB / T 6308-2006 open mill method, after mixing, the rotorless vulcanizer is used, according to the method of GB / T16584-1996, under the condition of 160℃, 30min, the vulcanization time is analyzed. At the same time, the Mooney viscosity of the mixed rubber is measured by GB / T 1232.1-2016 to characterize the plasticizing performance. The test results are shown in Table 33.

[0125] The formula is shown in the following table (unit PHR):

[0126] Table 18

[0127] Nitrile rubber, acrylonitrile content 33%, Mooney 55 100 parts by mass 8# standard carbon black 40 parts by mass Example 3 and comparative product or master batch 2 parts by mass

[0128] (II) Test method of masterbatch amount required for 20min vulcanization: according to the following Table 19 formula, the product of the example or the comparative example is mixed by GB / T 6308-2006 open mill method, after mixing, the rotorless vulcanizer is used, according to the method of GB / T16584-1996, under the condition of 160℃, 30min, the vulcanization time is analyzed. And adjust the amount of the product of Example 3 and the comparative example, to obtain the product amount when the vulcanization time is 20min. The test results are shown in Table 34.

[0129] The formula is shown in the following table (unit PHR):

[0130] Table 19

[0131] Nitrile rubber, acrylonitrile content 33%, Mooney 55 100 parts by mass 8# standard carbon black 40 parts by mass Example 3 and comparative product or master batch Adjust and determine

[0132] (III) Plasticizing performance test method: according to the following Table 20 formula, the product of the example or the comparative example is mixed by the GB / T 6308-2006 mill method, and then is parked at room temperature for 48 h, and the mixed glue Mooney viscosity is tested, so as to be taken as the representation of the plasticizing effect. The test result is shown in Table 35.

[0133] The formula is shown in the following table (unit: PHR):

[0134] Table 20

[0135] Nitrile rubber, acrylonitrile content 33%, Mooney 55 100 parts by mass 8# standard carbon black 40 parts by mass Example 3 and comparative product or master batch 3 parts by mass

[0136] Example 4

[0137] The formula is shown in the following table (unit PHR):

[0138] Table 21

[0139] Polyisobutylene (molecular weight 120000) 100 parts by mass 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane 40 parts by mass Accelerator DM 150 parts by mass Accelerator M 100 parts by mass Accelerator CZ 50 parts by mass Sulfur 600 parts by mass Zinc oxide 150 parts by mass Stearic acid 50 parts by mass Ethylene-propylene rubber 30 parts by mass

[0140] Operation process: the polyisobutylene, zinc oxide and stearic acid in the formula are put into the internal mixer for preliminary mixing, about 1 minute later, the accelerator, sulfur and 2,5-dimethyl-2,5-bis(tert-butyl peroxy hexane) are put in, and then the temperature of the internal mixer is controlled to be less than 100 DEG C, and then the mixed masterbatch is put into the extrusion granulator for granulation, and the prepared masterbatch is parked for 2 h, and then is placed in the temperature of 170 DEG C for 15 minutes, and then the product masterbatch is obtained.

[0141] Comparative example 4-1

[0142] The formula is shown in the following table (unit PHR):

[0143] Table 22

[0144]

[0145] Operation process: the polyisobutylene, zinc oxide and stearic acid in the formula are put into the internal mixer for preliminary mixing, about 1 minute later, the accelerator, sulfur and 2,5-dimethyl-2,5-bis(tert-butyl peroxy hexane) are put in, and then the temperature of the internal mixer is controlled to be less than 100 DEG C, and then the mixed masterbatch is put into the extrusion granulator for granulation, and the prepared masterbatch is parked for 2 h, and then the product masterbatch is obtained.

[0146] Comparative example 4-2

[0147] The formula is shown in the following table (unit PHR):

[0148] Table 23

[0149] Nitrile rubber 100 parts by mass 2,5-dimethyl-2,5-bis(hexane 40 parts by mass Accelerator DM 150 parts by mass Accelerator M 100 parts by mass Accelerator D 50 parts by mass Sulfur 600 parts by mass Zinc oxide 150 parts by mass Stearic acid 50 parts by mass Ethylene-propylene rubber 30 parts by mass

[0150] Process: Put the nitrile rubber, zinc oxide and stearic acid in the formula into the internal mixer for preliminary mixing, after about 1 minute, put the accelerator, sulfur and 2,5-dimethyl-2,5-bis(tert-butyl peroxy) hexane, and mix thoroughly, control the temperature of the internal mixer not to exceed 100℃, then discharge, then put the mixed masterbatch into the extrusion granulator for granulation, and then put the prepared masterbatch into the temperature of 170℃ for 15 minutes, and then the product masterbatch is obtained.

[0151] Comparative Example 4-3

[0152] According to the formula of Example 3, the product is obtained by simply mixing without granulation.

[0153] Test Example 4

[0154] (I) Analysis method of vulcanization speed: according to the following Table 24 formula, the product of the example or the comparative example is mixed by GB / T 6308-2006 open mill method, after mixing, the rotorless vulcanizer is used, according to the method of GB / T16584-1996, the vulcanization time is analyzed under the condition of 160℃, 30min. At the same time, the Mooney viscosity of the mixed rubber is measured by GB / T 1232.1-2016 to characterize the plasticizing performance. The test results are shown in Table 33.

[0155] The formula is shown in the following table (unit: PHR):

[0156] Table 24

[0157] Nitrile rubber, acrylonitrile content 33%, Mooney 55 100 parts by mass 8# standard carbon black 40 parts by mass Example 4 and comparative product or master batch 2 parts by mass

[0158] (II) Test method of the amount of masterbatch required for 20min vulcanization: according to the following Table 25 formula, the product of the example or the comparative example is mixed by GB / T 6308-2006 open mill method, after mixing, the rotorless vulcanizer is used, according to the method of GB / T16584-1996, the vulcanization time is analyzed under the condition of 160℃, 30min. And adjust the amount of the product of Example 4 and the comparative example, and the amount of the product when the vulcanization time is 20min is obtained. The test results are shown in Table 34.

[0159] The formula is shown in the following table (unit: PHR):

[0160] Table 25

[0161] Nitrile rubber, acrylonitrile content 33%, Mooney 55 100 parts by mass 8# standard carbon black 40 parts by mass Example 4 and comparative product or master batch Adjust and determine

[0162] (III) Plasticizing performance test method: according to the following table 26, the product of the example or the comparative example is mixed by the GB / T 6308-2006 mill method, then is parked for 48h at room temperature, and the mixed glue mooney viscosity is tested, so as to be taken as the representation of the plasticizing effect. The test result is shown in table 35.

[0163] The formula is shown in the following table (unit: PHR):

[0164] Table 26

[0165] Nitrile rubber, acrylonitrile content 33%, Mooney 55 100 parts by mass 8# standard carbon black 40 parts by mass Example 4 and comparative product or master batch 4 parts by mass

[0166] Example 5

[0167] The formula is shown in the following table (unit PHR):

[0168] Table 27

[0169] Polyisobutylene (molecular weight 40000) 100 parts by mass Di-tert-butyl peroxide 60 parts by mass Accelerator DM 250 parts by mass Accelerator M 200 parts by mass Accelerator D 50 parts by mass Sulfur 200 parts by mass

[0170] Operation process: the polyisobutylene in the formula is put into the internal mixer for preliminary mixing, the accelerator, sulfur and di-tert-butyl peroxide are put in after about 1 minute, and then the temperature of the internal mixer is controlled to be less than 100 DEG C, and then the material is discharged, and then the mixed masterbatch is put into the extrusion granulator for granulation, and the prepared masterbatch is parked for 2h, and then the temperature is controlled to be 150 DEG C for 20 minutes, and then the product masterbatch is obtained.

[0171] Comparative example 5-1

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

[0173] Table 28

[0174] Polyisobutylene (number average molecular weight 40000) 100 parts by mass Di-tert-butyl peroxide 60 parts by mass Accelerator DM 250 parts by mass Accelerator M 200 parts by mass Accelerator D 50 parts by mass Sulfur 200 parts by mass

[0175] Operation process: the polyisobutylene in the formula is put into the internal mixer for preliminary mixing, the accelerator, sulfur and di-tert-butyl peroxide are put in after about 1 minute, and then the temperature of the internal mixer is controlled to be less than 100 DEG C, and then the material is discharged, and then the mixed masterbatch is put into the extrusion granulator for granulation, and the prepared masterbatch is parked for 2h, and then the product masterbatch is obtained.

[0176] Comparative example 5-2

[0177] The formula is shown in the following table (unit PHR):

[0178] Table 29

[0179]

[0180]

[0181] Operation process: put the nitrile rubber in the formula into the internal mixer for preliminary mixing, put the accelerator and sulfur and di-t-butyl peroxide after about 1 minute, fully mix, control the temperature of the internal mixer not to exceed 100℃, then discharge, then put the mixed masterbatch into the extrusion granulator for granulation, put the prepared masterbatch into the temperature of 150℃ for 2h, then put it into the temperature of 150℃ for 20 minutes, then the product masterbatch is obtained.

[0182] Comparative example 5-3

[0183] According to the formula of example 5, the product is obtained by simply mixing without granulation.

[0184] Test example 5

[0185] (I) Analysis method of vulcanization speed: according to the following table 30 formula, the product of example or comparative example is mixed by GB / T 6308-2006 open mill method, after mixing, the rotorless vulcanization instrument is used, according to the method of GB / T16584-1996, under the condition of 160℃, 30min, the vulcanization time is analyzed. At the same time, the mooney viscosity of the mixed rubber is measured by GB / T 1232.1-2016 to characterize the plasticizing property. The test results are shown in table 33.

[0186] The formula is shown in the following table (unit PHR):

[0187] Table 30

[0188] Nitrile rubber, acrylonitrile content 33%, Mooney 55 100 parts by mass 8# standard carbon black 40 parts by mass Zinc oxide 3 parts by mass Stearic acid 1 part by mass Example 5 and comparative product or master batch 2 parts by mass

[0189] (II) Test method of masterbatch amount required for 20min vulcanization: according to the following table 31 formula, the product of example or comparative example is mixed by GB / T 6308-2006 open mill method, after mixing, the rotorless vulcanization instrument is used, according to the method of GB / T16584-1996, under the condition of 160℃, 30min, the vulcanization time is analyzed. And adjust the amount of example 5 and comparative example product, the amount of product when the vulcanization time is 20min is obtained. The test results are shown in table 34.

[0190] The formula is shown in the following table (unit PHR):

[0191] Table 31

[0192] Nitrile rubber, acrylonitrile content 33%, Mooney 55 100 parts by mass 8# standard carbon black 40 parts by mass Zinc oxide 3 parts by mass Stearic acid 1 part by mass Example 5 and comparative product or master batch Adjust and determine

[0193] (III) Test method of plasticizing property: according to the following table 32 formula, the product of example or comparative example is mixed by GB / T 6308-2006 open mill method, then it is placed at room temperature for 48h, the mooney viscosity of the mixed rubber is tested, which is used as the characterization of plasticizing effect. The test results are shown in table 35.

[0194] The formula is shown in the following table (unit PHR):

[0195] Table 32

[0196] Nitrile rubber, acrylonitrile content 33%, Mooney 55 100 parts by mass 8# standard carbon black 40 parts by mass Zinc oxide 3 parts by mass Stearic acid 1 part by mass Example 1 and comparative product or master batch 5 parts by mass

[0197] Performance comparison test results of test examples 1-5:

[0198] (I) The results of the positive curing time:

[0199] Table 33

[0200]

[0201]

[0202] From the curing speed, it can be seen that using the implementation method of the present application, compared with the comparative example, the curing speed can be significantly improved.

[0203] (II) The product dosage results (phr) for 20 min positive curing:

[0204] Table 34

[0205]

[0206]

[0207] From the product amount required for 20 min positive curing time, it can be seen that the master batch product prepared by the method of the present application greatly reduces the amount of vulcanizing aid used when achieving the same vulcanization effect.

[0208] (III) The analysis results of the mixing gum Mooney viscosity:

[0209] Table 36

[0210]

[0211]

[0212] From the mixing gum Mooney viscosity, it can be seen that the master batch prepared by the method of the present application can effectively reduce the Mooney viscosity of the rubber mixing gum, and has good plasticizing effect.

[0213] From the overall implementation effect, the full vulcanization system dispersion master batch with anti-bloom function prepared by the method provided by the present application has the characteristics of fast curing speed, less amount of vulcanizing aid, good anti-bloom effect and obvious plasticizing property.

[0214] Of course, the present application can have other various embodiments, and those skilled in the art can make various corresponding changes and modifications according to the present application without departing from the spirit and essence of the present application, and these corresponding changes and modifications shall all belong to the protection scope of the present application.

Claims

1. A plasticizing fully vulcanized system dispersion masterbatch, characterized in that, The raw material components include the following parts by weight: 100 parts of polyisobutylene 10-100 parts of peroxide containing tert-butyl groups. Sulfur 100-2000 parts, Accelerator 300-1000 parts; The preparation method of the dispersion masterbatch includes: (1) mixing polyisobutylene, tert-butyl peroxide, sulfur and accelerator, and then granulating to obtain primary masterbatch; (2) heating and aging the primary masterbatch after it has been left to stand to obtain dispersion masterbatch.

2. The dispersion masterbatch according to claim 1, characterized in that, The raw material components include the following parts by weight: 100 parts of polyisobutylene Peroxides containing tert-butyl groups, 30-70 parts Sulfur 200-800 parts, Accelerator 300-600 parts.

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

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

5. The dispersion masterbatch according to claim 1, characterized in that, The number-average molecular weight of the polyisobutylene is above 20,000.

6. The dispersion masterbatch according to claim 1, characterized in that, The tert-butyl-containing peroxide is selected from at least one of di-tert-butyl peroxide and 2,5-dimethyl-2,5-bis(tert-butyl peroxide)hexane.

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

8. The dispersion masterbatch according to claim 1, characterized in that, The mixing temperature shall not exceed 100°C.

9. The dispersion masterbatch according to claim 1, characterized in that, The settling time is 0.1-4 hours.

10. The dispersion masterbatch according to claim 1, characterized in that, The ripening conditions are: temperature 160-190℃, time 5-20 minutes.

Images