CN111607180A - Environment-friendly comprehensive accelerator pre-dispersed master batch and preparation method and application thereof - Google Patents
Environment-friendly comprehensive accelerator pre-dispersed master batch and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of rubber additives, and discloses an environment-friendly comprehensive accelerator pre-dispersed master batch particle, a preparation method and application thereof, wherein the master batch particle comprises the following components in parts by weight: 20-40 parts of a polymer carrier; 20-40 parts of pyrithione salt compounds; 10-25 parts of bicyclic amidine compounds; 2-5 parts of an organic acid compound; 10-20 parts of an inorganic filler; 2-10 parts of a plasticizer; 2-10 parts of a dispersing agent. The invention utilizes the synergistic use effect of the pyrithione compound, the bicyclic amidine compound and the organic acid compound, does not generate potential toxic substances such as nitrosamine and the like in the vulcanization process, has the characteristics of long scorching time, high vulcanization speed and reversion resistance, can be used for replacing the existing guanidine accelerators, does not contain carcinogenic components such as o-toluidine and the like in the use process, and is safe and environment-friendly.
Description
Technical Field
The invention relates to the technical field of rubber additives, in particular to an environment-friendly comprehensive accelerator pre-dispersed master batch and a preparation method and application thereof.
Background
The vulcanization accelerator of the rubber is an accelerator for short, can promote the vulcanization of the rubber, shorten the vulcanization time, reduce the vulcanization temperature, reduce the consumption of the vulcanizing agent, improve the physical and mechanical properties of the rubber and the like.
The acrylate rubber is a copolymer formed by copolymerizing an acrylate monomer and a small amount of monomers with crosslinking active groups, the main chain of the acrylate rubber is saturated, and the side group of the acrylate rubber contains polar ester groups, so that the acrylate rubber has excellent oxidation resistance, ozone resistance, oil resistance, high temperature resistance and other characteristics, and is widely applied to the fields of automobiles, electric appliances, trains, aviation and the like.
However, the acrylic rubber is usually vulcanized by diphenylguanidine, di-o-tolylguanidine and the like, but the guanidine accelerator and a vulcanizing agent react to generate a potential carcinogenic o-toluidine in the high-temperature vulcanization process, so that the development of an environment-friendly accelerator to replace the existing guanidine accelerator is a problem to be solved urgently in the rubber industry at present. Meanwhile, most of the existing accelerators are powder or liquid, and the problems of poor dispersibility, long mixing period, difficult metering, environmental pollution and the like exist in the actual use process.
CN105295275A discloses a pre-dispersed master batch particle of an acrylate rubber accelerator and a preparation method thereof, wherein the pre-dispersed master batch particle comprises the following components in parts by weight: 20-40 parts of acrylate polymer carrier, 10-25 parts of dialkyl dithiophosphate, 20-40 parts of diamine compound, 20-40 parts of inorganic filler and 1-10 parts of operating oil. When the pre-dispersed master batch particles are used for vulcanizing the acrylate rubber, compared with the existing acrylate rubber accelerator, the pre-dispersed master batch particles not only can keep the physical characteristics of the vulcanized acrylate rubber, but also are safe, environment-friendly and easy to disperse, can effectively improve the vulcanizing efficiency, optimize the scorching time, avoid the phenomenon of frost spraying and improve the low compression deformation and the aging resistance of rubber products.
However, when the comprehensive accelerator is used for pre-dispersing the masterbatch particles, the vulcanization speed of the rubber material is low, and the more appropriate vulcanization speed can be obtained only by greatly increasing the vulcanization temperature, but the heat conductivity coefficient of the rubber material is low, and the vulcanization time is prolonged by increasing the vulcanization temperature, so that the comprehensive accelerator is not suitable for being used as a vulcanization accelerator for large-size rubber products.
CN110591261A discloses a pre-dispersed master batch particle of a vulcanization crosslinking activator of acrylate rubber and a preparation method thereof, wherein the master batch particle comprises 50-60 parts of DBU, 12-20 parts of MMBI, 1-5 parts of high molecular weight unsaturated zinc salt, 5-10 parts of an ester plasticizer and 15-20 parts of acrylate rubber, the vulcanization activator enables DBU, MMBI and other components to be dispersed in the acrylate rubber more uniformly, the scorch resistance and compression permanent deformation of the acrylate rubber are effectively improved, and the vulcanization speed, the processing safety and the heat resistance and the aging resistance of vulcanized rubber of the acrylate rubber are further improved.
However, when the comprehensive accelerator is used for pre-dispersing the masterbatch particles, the accelerator can be decomposed to generate insoluble alkaline substances in the high-temperature vulcanization process, so that the surface blooming phenomenon of rubber products is easy to occur, and the quality and the performance of the rubber products are further influenced.
Disclosure of Invention
The invention aims to provide an environment-friendly comprehensive accelerator pre-dispersed master batch particle without guanidine compounds, the master batch particle is safe, non-toxic and good in dispersibility, and can effectively improve the vulcanization efficiency of acrylate rubber, optimize the scorching time, avoid the blooming phenomenon and improve the low compression deformation and aging resistance of rubber products.
In order to achieve the purpose, the invention adopts the technical scheme that:
the environment-friendly comprehensive accelerator pre-dispersed master batch comprises the following components in parts by weight:
the polymer carrier is acrylic rubber, and comprises any one or more of acrylate rubber, ethylene-acrylic acid copolymer, ethylene- (methyl) acrylate, ethylene-methyl acrylate copolymer and ethylene-ethyl acrylate copolymer.
The pyrithione salt compound is one or more of zinc pyrithione, molybdenum pyrithione, bismuth pyrithione, copper pyrithione and ferric pyrithione. As a novel vulcanization accelerator for rubber, no relevant report is found.
The bicyclic amidine compound comprises any one or more of 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU), 1, 5-diazabicyclo [4,3,0] non-5-ene (DBN) and 1,5, 7-triazabicyclo [4.4.0] dec-5-ene (TBD) and is used as a vulcanization accelerator of rubber.
The organic acid compound comprises any one or more of formic acid, acetic acid, octanoic acid, isooctanoic acid, benzoic acid, oleic acid, stearic acid, phenol and p-toluenesulfonic acid, and is used as an activator of a vulcanization accelerator of rubber.
The synergistic effect of the pyrithione compound, the bicyclic amidine compound and the organic acid compound is utilized, so that potential toxic substances such as nitrosamine and the like are not generated in the vulcanization process, and the vulcanization accelerator has the characteristics of long scorching time, high vulcanization speed and reversion resistance.
Preferably, the pyrithione compound is zinc pyrithione or molybdenum pyrithione, the bicyclic amidine compound is DBU or TBD, and the organic acid compound is isooctanoic acid or stearic acid, so that under the combination, the rubber compound after the pre-dispersed masterbatch particles are applied has longer scorching time, shorter vulcanization time and better mechanical property, and is even improved compared with the existing product.
Preferably, the weight ratio of the pyrithione compound to the bicyclic amidine compound to the organic acid compound is 3-8: 3-8: 1. when the pre-dispersed master batch obtained according to the proportion is applied, the rubber material has longer scorching time and better vulcanization reversion characteristic.
Further preferably, the weight ratio of the pyrithione compound, the bicyclic amidine compound and the organic acid compound is 4-5: 4-5: 1, the prepared pre-dispersed master batch has better effect.
The inorganic filler comprises any one or more of talcum powder, calcium carbonate, diatomite, white carbon black, clay and carbon black, is mainly used for adsorbing liquid components such as dicyclo amidine compounds and the like to prevent the dicyclo amidine compounds from being separated out, can also adjust the stiffness of the pre-dispersed masterbatch particles, and is beneficial to keeping the original shape of the pre-dispersed masterbatch particles.
The plasticizer is used for increasing the fluidity of the pre-dispersed rubber compound and comprises any one or more of phthalate esters, citrate esters, aliphatic dibasic acid esters and epoxidized soybean oil.
The dispersant is used for improving the dispersibility of powdery materials, and comprises any one or more of stearic acid, oleamide, erucamide, stearate and polyethylene wax.
Preferably, the pre-dispersed masterbatch particles can be added with coloring agents to distinguish the types of the pre-dispersed masterbatch particles by specific colors and increase the identification degree of the pre-dispersed masterbatch particles. The colorant includes, but is not limited to, organic colorants and/or inorganic colorants. Further preferably, the colorant is 0.01-0.1 part by weight.
The invention also provides a preparation method of the environment-friendly comprehensive accelerator pre-dispersed masterbatch particle, which comprises the following steps:
(1) accurately weighing the raw materials according to the proportion, and adding the polymer carrier and the plasticizer into an internal mixer for mixing;
(2) continuously adding inorganic filler and dispersant into the internal mixer for mixing;
(3) continuously adding the dicyclic amidine compound, the pyrithione salt compound and the organic acid compound into the internal mixer in sequence for mixing to obtain a pre-dispersed sizing material;
(4) and (4) extruding and granulating the pre-dispersed rubber material mixed in the step (3) in an extruder to obtain the environment-friendly comprehensive accelerator pre-dispersed masterbatch particles.
In the step (1), the mixing temperature is 50-150 ℃, the rotor speed is 60-120 r/min, and the mixing time is 5-20 min; further preferably 10-15 min;
in the step (2), the mixing temperature is 40-100 ℃, the rotor speed is 30-80 r/min, and the mixing time is 5-25 min; further preferably 10-15 min;
in the step (3), the mixing temperature is 40-80 ℃, the rotor speed is 40-80 r/min, and the mixing time is 3-25 min; 5-12 min;
in the step (4), the processing temperature of the extruder is 40-80 ℃, the rotating speed of the screw is 40-100 r/min, and the diameter of the obtained pre-dispersed masterbatch particles is 4-10 mm, and the length of the pre-dispersed masterbatch particles is 4-12 mm.
Preferably, in the step (4), a metal filter screen of 60-400 meshes is used for the pre-dispersed rubber material before entering the extruder, so as to further improve the dispersibility of each component in the pre-dispersed rubber material and remove particles.
Further preferably, in order to increase the identification degree of the pre-dispersed masterbatch particles, 0.01-0.1 part of colorant can be added in the step (3).
In order to solve the problems of poor dispersibility, long mixing period, difficult metering, environmental pollution and the like of the existing powdery or liquid vulcanization accelerator in the actual use process, the invention adopts mixing, extruding, filtering and granulating tools to pre-disperse the vulcanization accelerator, and forms environment-friendly comprehensive accelerator pre-dispersed masterbatch particles with high dispersibility, high activity, high uniformity and the like.
The environment-friendly comprehensive accelerator pre-dispersed masterbatch disclosed by the invention is applied to acrylate rubber as an accelerator, and 1-3 parts of the environment-friendly comprehensive accelerator pre-dispersed masterbatch is added to 100 parts of an acrylate rubber matrix.
The pre-dispersed masterbatch particles of the accelerator can obviously improve the vulcanization efficiency of the acrylate rubber, has the performance equivalent to that of a guanidine accelerator, not only can maintain the physical performance of the vulcanized acrylate rubber, but also can endow a rubber product with lower compression deformation and higher aging resistance, and simultaneously can eliminate or reduce the surface blooming phenomenon of the rubber product, so that the pre-dispersed masterbatch particles of the accelerator are a comprehensive accelerator which is environment-friendly and has higher comprehensive performance.
Compared with the prior art, the invention has the following beneficial effects:
(1) the accelerator pre-dispersed masterbatch particle can be used for replacing the existing guanidine accelerator, has no carcinogenic components such as o-toluidine and the like in the using process, is safe and environment-friendly, and eliminates the risk of generating carcinogens by the guanidine accelerator.
(2) The pre-dispersed master batch particles of the accelerator can improve the vulcanization efficiency of rubber compound, prolong the scorching time, eliminate the blooming phenomenon, and also can obviously improve the compression permanent deformation and the ageing resistance of vulcanized rubber.
(3) The organic acid compound in the accelerator pre-dispersed masterbatch particles can effectively prolong the scorching time in the rubber vulcanization process, remarkably improve the processing safety of rubber materials, particularly prevent the rubber materials from scorching in advance at the temperature higher than 80 ℃, and have the function of an anti-scorching agent. Meanwhile, the organic acid compound reacts with insoluble alkaline substances generated in the high-temperature vulcanization process, so that the bad phenomenon that products are easy to frost can be eliminated.
(4) The pyrithione salt compound in the pre-dispersed master batch particles of the accelerator is a novel accelerator which has the function of an anti-aging agent, can improve the anti-aging performance of vulcanized rubber, does not need to add the anti-aging agent in the rubber vulcanization process, and realizes the effect of one agent with multiple purposes.
(5) The accelerant is prepared into a pre-dispersed masterbatch particle type, and the problems of uneven dispersity, long mixing period, difficult metering and the like in the mixing process of the traditional accelerant are solved.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. Those skilled in the art should understand that they can make modifications and equivalents without departing from the spirit and scope of the present invention, and all such modifications and equivalents are intended to be included within the scope of the present invention.
The raw materials used in the following embodiments are all commercially available raw materials.
Example 1
The environment-friendly comprehensive accelerator pre-dispersed master colloidal particle comprises 35 parts of acrylate rubber, 17 parts of zinc pyrithione, 21 parts of DBU, 5 parts of isooctanoic acid, 13 parts of white carbon black, 5.9 parts of dioctyl phthalate, 3 parts of oleamide and 0.1 part of yellow colorant.
(1) Adding acrylate rubber and dioctyl phthalate into a pressure type internal mixer, and mixing for 7min under the conditions that the mixing temperature is 60 ℃ and the rotor speed is 50 r/min;
(2) adding white carbon black and oleamide into an internal mixer, and continuously mixing for 7min under the conditions that the mixing temperature is 60 ℃ and the rotor speed is 50 r/min;
(3) continuously adding zinc pyrithione, DBU, isooctanoic acid and yellow colorant into the internal mixer, and continuously mixing for 8min under the conditions that the mixing temperature is 70 ℃ and the rotor speed is 65r/min to prepare a pre-dispersed rubber material;
(4) and (3) adding the pre-dispersed rubber material obtained in the step (3) into a cold-feeding single-screw extruder, setting the processing temperature to be 60 ℃, the screw rotating speed to be 45r/min and the mesh number of a filter screen to be 120 meshes, and filtering, extruding and granulating to obtain particles with the diameter and the length of about 5mm, thereby obtaining the environment-friendly comprehensive accelerator pre-dispersed masterbatch particles.
The prepared environment-friendly comprehensive accelerator pre-dispersed master batch particles are detected and analyzed by a gas chromatography-mass spectrometer, and the test result shows that: no o-toluidine component was detected.
Application example 1
The environment-friendly comprehensive accelerator pre-dispersed masterbatch prepared in example 1 is added to acrylate rubber as an accelerator, and the existing product di-o-tolylguanidine (DOTG) is used as a comparison product to be vulcanized according to the proportion in Table 1.
TABLE 1 formulation of the components of the acrylate rubber vulcanization system
| Component (parts by weight) | Application example 1 | Comparative example 1 |
| Acrylate rubber | 100 | 100 |
| Carbon Black N550 | 50 | 50 |
| Stearic acid | 1.5 | 1.5 |
| Vulcanizing agent HMDC | 1 | 1 |
| DOTG | — | 2 |
| Example 1 product | 2 | — |
| Plasticizer TP95 | 1.6 | 1.6 |
And (3) detecting and analyzing the air in the car and the organic volatile matters of the car interior trim part material by using the vulcanized acrylate rubber, wherein the test result shows that: no o-toluidine component was detected. The rubber after vulcanization was tested for various properties, and the results of the property tests are shown in tables 2 and 3.
The test conditions for the sulfurization characteristics in Table 2 were 175 ℃ C. for 40min, MH-MLRepresents the degree of crosslinking of the rubber; t isC10Represents the scorch time; t isC90Indicating the process positive cure time. It can be seen from table 2 that the comprehensive accelerator pre-dispersed masterbatch prepared in example 1 can not only completely replace accelerator DOTG, but also improve the vulcanization efficiency and scorch performance of the rubber vulcanization system.
TABLE 2 Mooney viscosity and vulcanization characteristics of acrylate rubber under different vulcanization systems
| Performance parameter | Application example 1 | Comparative example 1 |
| Mooney viscosity, ML (1+4), 100 deg.C | 45.9 | 46.5 |
| TC10(min) | 4.31 | 3.83 |
| TC90(min) | 16.88 | 21.67 |
| MH-ML(dN·m) | 4.3 | 3.9 |
Table 3 shows the mechanical properties of the acrylate rubber under different vulcanization systems, and it can be seen from table 3 that the hardness, elongation at break, tensile strength and resilience of the environment-friendly comprehensive accelerator pre-dispersed masterbatch prepared in example 1 are substantially equivalent to those of the rubber vulcanized by DOTG, and the tear strength of the rubber vulcanized by the environment-friendly comprehensive accelerator pre-dispersed masterbatch prepared in example 1 is significantly improved, and the compression set is significantly reduced.
TABLE 3 mechanical Properties of acrylate rubbers under different vulcanization systems
Aging the vulcanized acrylate rubber at 150 ℃ for 72h, testing the mechanical properties of the acrylate rubber, comparing the changes of the mechanical properties before and after aging, and judging the thermal aging property of the acrylate rubber, wherein the results are shown in Table 4. As can be seen from Table 4, the acrylate rubber exhibits excellent heat aging properties in which hardness, tensile strength, elongation at break are not attenuated and compression set changes are small, using the comprehensive accelerator of example 1 instead of accelerator DOTG.
TABLE 4 thermal aging resistance of acrylate rubber under different vulcanization systems
| Performance parameter | Application example 1 | Comparative example 1 |
| Hardness Change Rate (%) | -0.9 | -3.2 |
| Tensile Strength Change Rate (%) | 3.1 | -3.2 |
| Elongation at Break Change (%) | 3.4 | -4.5 |
| Compression set change rate (%) | 0.7 | 3.7 |
Example 2
The environment-friendly comprehensive accelerator pre-dispersed master colloidal particle comprises 24 parts of ethylene-acrylate rubber, 23 parts of molybdenum pyrithione, 23 parts of TBD, 5 parts of stearic acid, 13 parts of calcium carbonate, 9 parts of acetyl tributyl citrate and 3 parts of erucamide. (1) Adding ethylene-acrylate rubber and acetyl tributyl citrate into a pressure type internal mixer, and mixing for 8min under the conditions that the mixing temperature is 100 ℃ and the rotor speed is 100 r/min;
(2) adding calcium carbonate and erucamide into an internal mixer, and continuously mixing for 10min under the conditions that the mixing temperature is 70 ℃ and the rotor speed is 60 r/min;
(3) continuously adding molybdenum pyrithione, 1,5, 7-triazabicyclo [4.4.0] dec-5-ene and stearic acid into an internal mixer, and continuously mixing for 10min under the conditions that the mixing temperature is 85 ℃ and the rotor speed is 50r/min to prepare a pre-dispersion rubber material;
(4) and (3) adding the pre-dispersed rubber material obtained in the step (3) into a cold-feeding single-screw extruder, setting the processing temperature to be 75 ℃, the screw rotating speed to be 50r/min and the mesh number of a filter screen to be 150 meshes, filtering, extruding and granulating to obtain particles with the diameter and the length of about 6mm, thereby obtaining the environment-friendly comprehensive accelerator pre-dispersed masterbatch particles. The prepared environment-friendly comprehensive accelerator pre-dispersed master batch particles are subjected to organic volatile detection analysis by a gas chromatography-mass spectrometer, and the test result shows that: no o-toluidine component was detected.
Application example 2
The environment-friendly comprehensive accelerator pre-dispersed masterbatch prepared in example 2 was added to ethylene-acrylate rubber as an accelerator, and the existing product Diphenylguanidine (DTG) was used as a comparison, and vulcanized according to the ratio in table 5.
TABLE 5 component formulation for ethylene-acrylate rubber vulcanization system
| Component (parts by weight) | Application example 2 | Comparative example 2 |
| Ethylene-acrylate rubber | 100 | 100 |
| Fumed silica | 50 | 50 |
| Stearic acid | 1 | 1 |
| Vulcanizing agent HMDC | 1.2 | 1.2 |
| DTG | — | 1.5 |
| EXAMPLE 2 product | 1.5 | — |
| Dibutyl citrate | 2 | 2 |
The vulcanized ethylene-acrylate rubber is subjected to detection and analysis on air in the car and organic volatile matters in car interior trim materials, and test results show that: no o-toluidine component was detected. The rubber after vulcanization was tested for various properties, and the results of the property tests are shown in tables 6 and 7.
The test conditions for the sulfurization characteristics in Table 6 were 175 ℃ C. for 40min, MH-MLRepresents the degree of crosslinking of the rubber; t isC10Represents the scorch time; t isC90Indicating the process positive cure time. From table 6, it can be seen that the comprehensive accelerator pre-dispersed masterbatch prepared in example 1 can not only completely replace the accelerator DTG, but also improve the vulcanization efficiency and scorch performance of the rubber vulcanization system.
TABLE 6 Mooney viscosity and vulcanization characteristics of ethylene-acrylate rubber under different vulcanization systems
| Performance parameter | Application example 2 | Comparative example 2 |
| Mooney viscosity, ML (1+4), 100 deg.C | 46.3 | 47.5 |
| TC10(min) | 1.13 | 0.72 |
| TC90(min) | 13.19 | 16.23 |
| MH-ML(dN·m) | 6.8 | 4.2 |
Table 7 shows the mechanical properties of ethylene-acrylate rubbers in different vulcanization systems, and it can be seen from table 7 that the hardness, tear strength, and resilience of the rubber vulcanized by using the environmentally friendly comprehensive accelerator pre-dispersed masterbatch particle prepared in example 2 and the DTG are substantially equivalent, and that the tensile strength and fracture productivity of the rubber vulcanized by using the environmentally friendly comprehensive accelerator pre-dispersed masterbatch particle prepared in example 2 are significantly improved, and the compression set is significantly reduced.
TABLE 7 mechanical Properties of ethylene-acrylate rubber under different vulcanization systems
The vulcanized ethylene-acrylate rubber is aged for 72 hours at 150 ℃, the mechanical properties of the ethylene-acrylate rubber are tested, the changes of the mechanical properties before and after aging are compared, the thermal aging properties of the ethylene-acrylate rubber are judged, and the results are shown in table 8. As can be seen from Table 8, the ethylene-acrylate rubber exhibits excellent heat aging properties in which hardness, tensile strength, and elongation at break are small, using the comprehensive accelerator of example 2 instead of the accelerator DTG.
TABLE 8 thermal aging resistance of ethylene-acrylate rubber under different vulcanization systems
| Performance parameter | Application example 2 | Comparative example 2 |
| Hardness Change Rate (%) | -2 | -8 |
| Tensile Strength Change Rate (%) | -5 | -21 |
| Elongation at Break Change (%) | 6.1 | -13 |
| Compression set change rate (%) | 0.7 | 3.7 |
Claims (10)
1. The environment-friendly comprehensive accelerator pre-dispersed master batch is characterized by comprising the following components in parts by weight:
2. the environment-friendly comprehensive accelerator pre-dispersed masterbatch particle as claimed in claim 1, wherein the polymer carrier comprises any one or more of acrylate rubber, ethylene-acrylic acid copolymer, ethylene- (meth) acrylate, ethylene-methyl acrylate copolymer, and ethylene-ethyl acrylate copolymer.
3. The environment-friendly comprehensive accelerator pre-dispersed masterbatch according to claim 1, wherein the pyrithione-based compound comprises one or more of zinc pyrithione, molybdenum pyrithione, bismuth pyrithione, copper pyrithione, and iron pyrithione.
4. The environment-friendly type comprehensive accelerator pre-dispersed masterbatch according to claim 1, wherein the dicyclic amidine compound comprises any one or more of 1, 8-diazabicyclo [5.4.0] undec-7-ene, 1, 5-diazabicyclo [ 4.3, 0] non-5-ene and 1,5, 7-triazabicyclo [4.4.0] dec-5-ene.
5. The environment-friendly comprehensive accelerator pre-dispersed masterbatch according to claim 1, wherein the organic acid compound comprises any one or more of formic acid, acetic acid, octanoic acid, benzoic acid, oleic acid, stearic acid, phenol, and p-toluenesulfonic acid.
6. The environment-friendly comprehensive accelerator pre-dispersed masterbatch particles according to claim 1, wherein the pyrithione compound is zinc pyrithione or molybdenum pyrithione, the dicyclamidine compound is 1, 8-diazabicyclo [5.4.0] undec-7-ene or 1,5, 7-triazabicyclo [4.4.0] dec-5-ene, and the organic acid compound is isooctanoic acid or stearic acid.
7. The environment-friendly comprehensive accelerator pre-dispersed masterbatch particle as claimed in claim 1, wherein the weight parts of the pyrithione compound, the bicyclic amidine compound and the organic acid compound are 3-8: 3-8: 1.
8. the preparation method of the environment-friendly comprehensive accelerator pre-dispersed masterbatch particle as claimed in any one of claims 1 to 7, which is characterized by comprising the following steps:
(1) accurately weighing the raw materials according to the proportion, and adding the polymer carrier and the plasticizer into an internal mixer for mixing;
(2) continuously adding inorganic filler and dispersant into the internal mixer for mixing;
(3) continuously adding the dicyclic amidine compound, the pyrithione salt compound and the organic acid compound into the internal mixer in sequence for mixing to obtain a pre-dispersed sizing material;
(4) and (4) extruding and granulating the pre-dispersed rubber material mixed in the step (3) in an extruder to obtain the environment-friendly comprehensive accelerator pre-dispersed masterbatch particles.
9. The preparation method of the environment-friendly comprehensive accelerator pre-dispersed masterbatch particle according to claim 8, which is characterized in that,
in the step (1), the mixing temperature is 50-150 ℃, the rotor speed is 60-120 r/min, and the mixing time is 5-20 min;
in the step (2), the mixing temperature is 40-100 ℃, the rotor speed is 30-80 r/min, and the mixing time is 5-25 min;
in the step (3), the mixing temperature is 40-80 ℃, the rotor speed is 40-80 r/min, and the mixing time is 3-25 min;
in the step (4), the processing temperature of the extruder is 40-80 ℃, and the rotating speed of the screw is 40-100 r/min.
10. The application of the environment-friendly comprehensive accelerator pre-dispersed masterbatch in the acrylate rubber as claimed in claims 1 to 7, wherein 1 to 3 parts of the environment-friendly comprehensive accelerator pre-dispersed masterbatch is added to 100 parts of the acrylate rubber matrix.
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| CN113563682A (en) * | 2021-08-25 | 2021-10-29 | 山东海益橡胶科技有限公司 | Modified carboxyl acrylate rubber without guanidine accelerator and preparation method thereof |
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