CN108610562B - Low-pressure-change high-temperature-resistant ethylene propylene rubber material and preparation method thereof - Google Patents
Low-pressure-change high-temperature-resistant ethylene propylene rubber material and preparation method thereof Download PDFInfo
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/244—Stepwise homogeneous crosslinking of one polymer with one crosslinking system, e.g. partial curing
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- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
Abstract
The invention discloses a low-pressure-change high-temperature-resistant ethylene propylene rubber material and a preparation method thereof, belonging to the technical field of rubber. The rubber material comprises the following components in parts by weight: 100 parts of ethylene propylene rubber raw rubber, 5 parts of zinc oxide, 1.2 parts of stearic acid, 4452 parts of an anti-aging agent, 4-8 parts of Ative CHO, 45-55 parts of fast extrusion carbon black N550, 25505-10 parts of a softening plasticizer S, 1.5-2.0 parts of a crosslinking assistant N308E 1.5 and 456.0-8.0 parts of a vulcanizing agent GF-GF. The rubber material disclosed by the invention has excellent high-temperature resistance, can have good physical properties after aging at 175 ℃, has the remarkable advantage of low compression set, and meets the performance requirements of German popular PV3330 and PV3307 standards on compression set.
Description
Technical Field
The invention belongs to the technical field of rubber, and particularly relates to a low-pressure-change high-temperature-resistant ethylene propylene rubber material and a preparation method thereof.
Background
The requirements of the ethylene propylene rubber sealing element on high temperature resistance and low compression permanent deformation performance of ethylene propylene rubber materials are higher and higher. The performance of the rubber sealing element directly influences the sealing performance of the rubber sealing element. High-temperature-resistant ethylene propylene rubber is often applied to a cooling system of an automobile, and low compression set is one of the most key technical indexes of a rubber sealing element.
The detection standards of ethylene propylene rubber sealing parts are national standard pressure change (GB/T7759) and international pressure change (ISO815), the GB/T7759 and ISO815 test methods require that a sample is taken out of a high-temperature box and cooled, a compression clamp is loosened, the compression permanent deformation of the sample is measured after the sample is recovered for 30 minutes, and the Germany public company adopts PV3330 and PV3307 standards for the detection of ethylene propylene rubber materials, and the test methods of the two detection standards are more strict. The German popular PV3330 is that after the sample is taken out from the high temperature box and cooled to the room temperature, the compression clamper is loosened for 20 seconds to complete the experiment, and the compression permanent deformation of the PV3330 is required to be less than 40 percent after the hot air aging at 150 ℃ for 24 hours; for the viscoelastic material such as rubber, most samples cannot recover within 20 seconds at all, so the performance requirement on the ethylene propylene rubber material is higher; the PV3307 of Germany is that after the sample is aged at 150 ℃ for 24h and taken out from a high-temperature box to be cooled to room temperature, the compression clamper is released to complete the experimental test within 5 seconds, the PV3307 compression permanent deformation is required to be less than 60 percent, the requirement is more strict than that of the PV3330 experimental method, the performance requirement on the ethylene-propylene rubber material is higher, the requirement on the PV3307 compression permanent deformation of the ethylene-propylene rubber material is improved to be less than 42 percent by customers, and the difficulty is self-evident.
Chinese patent application No. 201710492764.0, publication No. CN107090133A discloses an ethylene propylene rubber material for a sealing element of an automobile heat dissipation system and a production method thereof, wherein the rubber material comprises the following components in parts by weight: 100 parts of ethylene propylene rubber raw rubber, 5 parts of zinc oxide, 0.5-1.5 parts of stearic acid, 3-6 parts of an anti-aging agent, 20-30 parts of fast extrusion carbon black N550, 10-20 parts of semi-reinforcing carbon black N77410, 3.5-7 parts of a crosslinking assistant Ricon 153D and 5-8.5 parts of a vulcanizing agent Perkadox 14-40B-GR. The rubber material has excellent high temperature resistance, can be used for a long time at the temperature of between 50 ℃ below zero and 150 ℃, and has the remarkable advantages of low temperature resistance and low compression permanent deformation. However, the compression set performance test of the rubber material is carried out by adopting the German popular PV3307 standard, and the compression set of the PV3307 is 42.6-45.6% after the rubber material is aged by hot air at 150 ℃ for 24h, so that the ethylene propylene rubber material sealing element prepared by adopting the components and the method can hardly meet the strict requirement of the invention on the compression set of the PV3307 of less than 42%. In the application, softening plasticizer is not used for obtaining low compression set performance, and the prepared ethylene propylene rubber material has difficulty in obtaining better process flowability.
Chinese patent application No. 201210038982.4, publication No. CN103254511A discloses an ethylene-propylene-diene monomer rubber, which is a product formed by mixing and vulcanizing a composition containing an ethylene-propylene-diene monomer rubber compound, a vulcanizing agent, a vulcanization activator system, an accelerator, a reinforcing agent and a softening plasticizer, wherein the vulcanizing agent is insoluble sulfur and/or pre-dispersed sulfur, the vulcanization activator system contains a component A and stearic acid, the component A is selected from active zinc oxide and/or pre-dispersed zinc oxide, in the composition, relative to 100 parts by weight of the ethylene-propylene-diene monomer rubber compound, the content of the vulcanizing agent is 0.5-4.5 parts by weight, the content of the vulcanization activator system is 4-13 parts by weight, the content of the accelerator is 3-10 parts by weight, the content of the reinforcing agent is 40-90 parts by weight, and the content of the softening plasticizer is 5-60 parts by weight, the weight ratio of the component A to the stearic acid is 1-10: 1. The optimized ethylene propylene diene rubber provided by the invention does not bloom, does not generate nitrosamine and has good mechanical property. However, the application uses 45-55 parts of softening plasticizer and common sulfur vulcanization system, which can cause the compression set property to be poor and is difficult to endure high temperature of 175 ℃, so that the ethylene propylene rubber material sealing element prepared by adopting the components and the method can hardly meet the detection standards of the German public company on the PV3330 and PV3307 of the ethylene propylene rubber material and the high temperature resistance requirements.
Therefore, it is a problem to be solved that the ethylene-propylene rubber sealing member meeting the PV3330 and PV3307 standards of the germany public and resisting the high temperature of 175 ℃ can be prepared by adjusting the components and the mixing method of the ethylene-propylene rubber material.
Disclosure of Invention
1. Problems to be solved
Aiming at the problem that the components and the mixing method of the existing ethylene propylene rubber material can not meet the standard requirements of the German masses PV3330 and PV3307, the invention provides a low-pressure-change high-temperature-resistant ethylene propylene rubber material meeting the standard requirements of the German masses PV3330 and PV3307 and a preparation method thereof.
2. Technical scheme
In order to solve the above problems, the present invention adopts the following technical solutions.
The low-pressure-change high-temperature-resistant ethylene propylene rubber material comprises the following components in parts by weight:
ethylene propylene rubber crude rubber 100 parts
5 portions of zinc oxide
Stearic acid 1.2 parts
2 portions of anti-aging agent
4-8 parts of vulcanization activator Ative CHO
45-55 parts of fast extrusion carbon black
5-10 parts of softening plasticizer
1.5-2.0 parts of crosslinking assistant
6.0-8.0 parts of a vulcanizing agent.
Preferably, the vulcanizing activator Ative CHO is a vulcanizing activator containing surface-modified treated calcium hydroxide.
Preferably, the ash content of the vulcanization activator Ative CHO is 69-74%, and the appearance of the vulcanization activator is white powder.
Preferably, the vulcanizing activator Ative CHO is a crosslinking activator and an acid acceptor produced by Kunshan Attman chemical Co.
Preferably, the ratio of the crosslinking assistant N308E to the vulcanizing agent GF-45 is 1: 4.
Preferably, the ethylene-propylene rubber raw rubber is Keltan 2750 produced by Langshen chemistry, and comprises the components of 48% of ethylene content, 7.8% of ENB third monomer content and narrow molecular weight distribution.
Preferably, the addition ratio of the ethylene propylene rubber crude rubber Keltan 2750 to the vulcanization activator Ative CHO is 100: (4-6).
Preferably, the addition ratio of the anti-aging agent 445 and the vulcanizing activator Ative CHO is 1: (2-3).
A preparation method of a low-pressure-change high-temperature-resistant ethylene propylene rubber material comprises the following steps:
step one, preparing master batch rubber: preparing materials according to the formula of the low-pressure variable high-temperature-resistant ethylene propylene rubber material, putting all raw materials except the crosslinking assistant N308E, the vulcanizing agents GF-45 and the Ative CHO with the dosage of 1/2 into an internal mixer, and discharging rubber at the temperature of 145 ℃ to obtain master batch;
step two, vulcanizing the master batch for the second time: putting the master batch obtained in the step one, a crosslinking assistant N308E, a vulcanizing agent GF-45 and an Ative CHO with the dosage of 1/2 into an internal mixer for internal mixing and vulcanizing, and discharging rubber when the temperature reaches 125-135 ℃;
step three, vulcanization: and (3) filling the molded rubber compound after the second-stage vulcanization into a mold, performing primary vulcanization on the rubber compound at 175-185 ℃ for 8min on a vulcanizing machine, and performing secondary treatment on the rubber compound at 150-155 ℃ for 3h + (180-185 ℃) for 1h to obtain a vulcanized rubber finished product.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention relates to a low-pressure-change high-temperature-resistant ethylene propylene rubber material, which is added with Ative CHO and has the following principle: in the vulcanization process of the ethylene propylene rubber material, the peroxide vulcanizing agent is used, so that acid molecules are generated in the crosslinking process, and the acid molecules have an inhibiting effect on crosslinking reaction, so that the use efficiency of the vulcanizing agent is reduced, and finally, the ethylene propylene rubber has poor pressure deformation performance and poor high temperature resistance; the invention adds Ative CHO which is a cross-linking activator containing calcium hydroxide with surface modification treatment, a vulcanization activator and an acid-absorbing agent, and can neutralize and absorb acidic byproducts generated in the cross-linking reaction to generate salt which does not affect the vulcanization performance and the vulcanization degree, so that more carbon-oxygen bonds which are not easy to be oxidized and broken can be generated between a peroxide vulcanizing agent and rubber, the activity of the cross-linking reaction generated between the peroxide vulcanizing agent and ethylene propylene rubber is improved, the actual use efficiency of the vulcanizing agent is improved, the cross-linking density is deepened, a network structure formed after the cross-linking reaction is firmer, and the high-temperature vulcanized rubber still has excellent performance after being resistant to the high temperature of 175 ℃.
(2) The difference between the modified calcium hydroxide-containing vulcanizing active agent Ative CHO used in the invention and the calcium hydroxide or calcium oxide added in the traditional process is that firstly, the calcium hydroxide and calcium oxide are easy to absorb moisture and agglomerate in the air, while the ash content of the vulcanizing active agent Ative CHO is 69-74%, and the calcium hydroxide contained in the vulcanizing active agent is not easy to agglomerate and absorb moisture after being modified; secondly, the calcium hydroxide and the calcium oxide are difficult to disperse in the rubber material, while the vulcanizing activator Ative CHO with the ash content of 69-74% has better dispersibility in the rubber material and is more uniform, so that the vulcanizing activator Ative CHO can better absorb acidic substances and improve the activity of the vulcanizing agent.
(2) The softening plasticizer is added in the formula, under the normal condition, the addition of the softening plasticizer can improve the technical performance of the ethylene propylene rubber, but the softening plasticizer can reduce the crosslinking density to further deteriorate the pressure-variable performance of the ethylene propylene rubber, and the influence of reducing the crosslinking density caused by adding the softening plasticizer can be counteracted by using the Ative CHO.
(3) According to the invention, the crosslinking assistant N308E and the vulcanizing agent GF-45 in a specific proportion relationship are used, so that the activity of the vulcanizing agent can be exerted to the maximum extent, the maximum crosslinking reaction between the vulcanizing agent and each component is promoted, and the ethylene propylene rubber material is provided with better mechanical property for resisting the high temperature of 175 ℃; reduces the generation of peroxide vulcanization residues, is more beneficial to improving the heat resistance of the ethylene propylene rubber material and obtains lower compression set performance.
(4) The specific proportion relationship of the vulcanizing agent and the crosslinking assistant, the proportion of the Ative CHO and the raw rubber, and the specific proportion of the Ative CHO and the anti-aging agent are matched with each other to generate a synergistic effect, and the prepared ethylene propylene rubber material has the characteristics of 175 ℃ high temperature resistance and low pressure denaturation resistance by combining secondary treatment processes with different temperatures in the preparation method.
(5) According to the PV3330 standard test, after aging at 150 ℃ for 24h, the sealing element made of the low-voltage variable high-temperature-resistant ethylene propylene rubber material in the embodiment 3 of the invention has a compression set of 32.6 percent, and meets the requirement that the compression set of German popular PV3330 is less than 40 percent, while the comparative example 1 without adding the vulcanization activator Ative CHO has a compression set of 53.8 percent under the same conditions and cannot meet the requirement that the compression set of German popular PV3330 is less than 40 percent; the sealing element made of the low-voltage variable high-temperature-resistant ethylene propylene rubber material in the embodiment 3 is tested by the PV3307 standard, after aging at 150 ℃ for 24h, the compression set is 35.6 percent, which meets the requirement that the compression set of the German popular PV3307 is less than 42 percent, while the comparative example 1 without adding the vulcanization activator Ative CHO has the compression set of 63.5 percent under the same condition, which can not meet the requirement that the compression set of the German popular PV3307 is less than 42 percent;
(6) according to the preparation method of the low-pressure-change high-temperature-resistant ethylene propylene rubber material, the master batch with a specific formula is subjected to primary treatment for 3h at 150-155 ℃ and secondary treatment for 1h at 180-185 ℃, residual micromolecular substances in a crosslinking reaction can be effectively removed, the crosslinking density is further deepened, and better low-compression permanent deformation performance is obtained;
(7) the invention relates to a preparation method of a low-pressure-change high-temperature-resistant ethylene propylene rubber material, wherein a vulcanization activator Ative CHO is divided into two batches for adding, firstly, only a master batch containing 1/2 dosage Ative CHO is added into an internal mixer to obtain a master batch, and the reason is that the added 1/2Ative CHO can be well dispersed in the master batch, and the other half of Ative CHO and a vulcanizing agent which are added later can be promoted to be rapidly dispersed during vulcanization due to the self dispersing homogenizing effect of the master batch to obtain the master batch; and then the master batch, the crosslinking assistant N308E, the vulcanizing agent GF-45 and the Ative CHO with the dosage of 1/2 are put into an internal mixer together for banburying and vulcanizing, so that the dispersion time of the vulcanizing agent in the master batch is greatly reduced, the vulcanization accelerator and other compounding agents can be uniformly dispersed in the rubber material, and the improvement of the compression permanent deformation performance of the ethylene propylene rubber material is facilitated.
(8) The key characteristics required by the material standard in the invention are that the technical index requirements after aging of 1 and high temperature resistance of 175 ℃ multiplied by 168h hot air are almost the same as those before aging.
Detailed Description
The invention is further described with reference to specific examples.
The ethylene propylene rubber raw rubber in the following examples is Keltan 2750 produced by Langshen chemistry; n550 is N550 fast extrusion carbon black produced by Cabot corporation; the zinc oxide is indirect zinc oxide produced by Zhenjiang white water chemistry limited company; stearic acid is produced by southern grease of malaysia; the anti-aging agent 445 is made by Jiangsu Huada chemical group limited company (CAS number: 10081-67-1); the supplier of softening plasticizer S2550 was shanghai Son association chemical; the suppliers of the crosslinking assistant N308E and the vulcanizing agent GF-45 are Shanxi Lang Rui company, and Ative CHO is a crosslinking activator acid acceptor produced by Kunshan Atman chemical Co.
Example 1
The low-pressure-change high-temperature-resistant ethylene propylene rubber material comprises the following components:
100 parts of ethylene propylene rubber raw rubber, 5 parts of zinc oxide, 1.2 parts of stearic acid, 4452 parts of anti-aging agent, 6 parts of Ative CHO, N55055 parts of fast extrusion carbon black, S255010 parts of softening plasticizer, N308E 1.5.5 parts of crosslinking assistant and GF-456.0 parts of vulcanizing agent.
The preparation method of the low-pressure-change high-temperature-resistant ethylene propylene rubber material comprises the following steps of:
step one, preparing master batch rubber: preparing materials according to a formula of a low-pressure variable high-temperature-resistant ethylene propylene rubber material, putting all raw materials except for crosslinking assistant N308E, vulcanizing agent GF-45 and Ative CHO (ethylene propylene rubber) with the dosage of 1/2 into an internal mixer, and discharging rubber at the temperature of 145 ℃ to obtain master batch;
step two, vulcanizing the master batch for the second time: putting the master batch obtained in the step one, the crosslinking assistant N308E, the vulcanizing agent GF-45 and the Ative CHO with the dosage of 1/2 into an internal mixer for internal mixing and vulcanizing, and discharging rubber when the temperature reaches 125 ℃;
step three, vulcanization: and (3) filling the molded rubber compound after the second-stage vulcanization into a mold, performing primary vulcanization on the rubber compound at 185 ℃ for 8min on a vulcanizing machine, and performing secondary treatment on the rubber compound at 150 ℃ for 3h +185 ℃ for 1h to obtain a vulcanized rubber finished product.
Example 2
The low-pressure-change high-temperature-resistant ethylene propylene rubber material comprises the following components:
100 parts of ethylene propylene rubber raw rubber, 5 parts of zinc oxide, 1.2 parts of stearic acid, 4452 parts of anti-aging agent, 8 parts of Ative CHO, 50 parts of fast extrusion carbon black N550, 25507 parts of softening plasticizer S, 1.8 parts of crosslinking assistant N308E 1.8 and 457-2 parts of vulcanizing agent GF.
The preparation method of the low-pressure-change high-temperature-resistant ethylene propylene rubber material comprises the following steps of:
step one, preparing master batch rubber: preparing materials according to a formula of a low-pressure variable high-temperature-resistant ethylene propylene rubber material, putting all raw materials except for crosslinking assistant N308E, vulcanizing agent GF-45 and Ative CHO (ethylene propylene rubber) with the dosage of 1/2 into an internal mixer, and discharging rubber at the temperature of 145 ℃ to obtain master batch;
step two, vulcanizing the master batch for the second time: putting the master batch obtained in the step one, the crosslinking assistant N308E, the vulcanizing agent GF-45 and the Ative CHO with the dosage of 1/2 into an internal mixer for internal mixing and vulcanizing, and discharging rubber when the temperature reaches 130 ℃;
step three, vulcanization: and (3) filling the molded rubber compound after the second-stage vulcanization into a mold, performing primary vulcanization at 175 ℃ for 8min on a vulcanizing machine, and performing secondary treatment under the conditions of 155 ℃ for 3h +180 ℃ for 1h to obtain a vulcanized rubber finished product.
Example 3
The low-pressure-change high-temperature-resistant ethylene propylene rubber material comprises the following components:
100 parts of ethylene propylene rubber raw rubber, 5 parts of zinc oxide, 1.2 parts of stearic acid, 4452 parts of an anti-aging agent, 4 parts of Ative CHO, N55045 parts of fast extrusion carbon black, S25505 parts of a softening plasticizer, N308E 2.0.0 parts of a crosslinking assistant and GF-458.0 parts of a vulcanizing agent.
The preparation method of the low-pressure-change high-temperature-resistant ethylene propylene rubber material comprises the following steps of:
step one, preparing master batch rubber: preparing materials according to a formula of a low-pressure variable high-temperature-resistant ethylene propylene rubber material, putting all raw materials except for crosslinking assistant N308E, vulcanizing agent GF-45 and Ative CHO (ethylene propylene rubber) with the dosage of 1/2 into an internal mixer, and discharging rubber at the temperature of 145 ℃ to obtain master batch;
step two, vulcanizing the master batch for the second time: putting the master batch obtained in the step one, the crosslinking assistant N308E, the vulcanizing agent GF-45 and the Ative CHO with the dosage of 1/2 into an internal mixer for internal mixing and vulcanizing, and discharging rubber when the temperature reaches 135 ℃;
step three, vulcanization: and (3) filling the molded rubber compound after the second-stage vulcanization into a mold, performing primary vulcanization at 180 ℃ for 8min on a vulcanizing machine, and performing secondary treatment under the conditions of 153 ℃ for 3h and 183 ℃ for 1h to obtain a vulcanized rubber finished product.
Comparative example 1
In comparative example 1, the formulation ingredients and preparation were the same as in example 3 except that Ative CHO was not added.
Comparative example 2
The rubber material prepared in the prior art of Chinese patent application No. 201710492764.0, publication No. CN107090133A and examples 1-4 adopts German popular PV3307 standard to carry out compression set performance test, and after aging in hot air at 150 ℃ for 24h, the compression set of PV3307 is 42.6% -45.6%, and all the compression sets are more than 42%.
TABLE 1 Performance test data of the rubber materials of the present invention
As can be seen from Table 1, the properties of the ethylene-propylene rubber material prepared by the invention are obviously superior to the technical index value, and the comprehensive properties of the embodiment 3 are optimal. When Ative CHO was not added, an ethylene-propylene rubber material satisfying the high temperature resistance of 175 ℃ and having a low compression set could not be obtained as in comparative example 1.
The PV3330 and PV3307 standard compression set data of comparative example 1 and example 3 show that the addition of Ative CHO has a large influence on the compression set performance of the ethylene-propylene rubber material, so that the vulcanization degree of the ethylene-propylene rubber material can be deepened, the heat aging resistance can be improved, and the ethylene-propylene rubber material has good physical performance.
The compression set data of the PV3330 and PV3307 standards used in comparative example 2 and example 3 show that the compression set performance of the conventional process formula ethylene-propylene rubber material can hardly reach the compression set < 42% standard without adding AtiveCHO vulcanization activator.
Claims (1)
1. The low-pressure-change high-temperature-resistant ethylene propylene rubber material is characterized by comprising the following components in parts by weight:
ethylene propylene rubber crude rubber 100 parts
5 portions of zinc oxide
Stearic acid 1.2 parts
4452 parts of anti-aging agent
4-8 parts of vulcanization activator Ative CHO
45-55 parts of fast extrusion carbon black
5-10 parts of softening plasticizer
1.5-2.0 parts of crosslinking assistant N308E 1.5
GF-456-8 parts of vulcanizing agent;
the vulcanizing activator Ative CHO is a vulcanizing activator containing calcium hydroxide subjected to surface modification treatment;
the ash content of the vulcanizing activator Ative CHO is 69-74%;
the preparation method of the low-pressure variable high-temperature-resistant ethylene propylene rubber material comprises the following steps:
step one, preparing master batch rubber: preparing materials according to a formula, putting all raw materials except the crosslinking assistant N308E, the vulcanizing agent GF-45 and the Ative CHO with the dosage of 1/2 into an internal mixer, and discharging rubber at the temperature of 145 ℃ to obtain master batch;
step two, vulcanizing the master batch for the second time: putting the master batch obtained in the step one, a crosslinking assistant N308E, a vulcanizing agent GF-45 and an Ative CHO with the dosage of 1/2 into an internal mixer for internal mixing and vulcanizing, and discharging rubber when the temperature reaches 125-135 ℃;
step three, vulcanization: filling the molded rubber compound subjected to secondary vulcanization into a mold, and carrying out primary vulcanization on the rubber compound at 175-185 ℃ for 8min on a vulcanizing machine; then carrying out secondary treatment under the conditions of: vulcanizing at 150-155 ℃ for 3h, and vulcanizing at 180-185 ℃ for 1h to obtain a vulcanized rubber finished product;
the ratio of the crosslinking assistant N308E to the vulcanizing agent GF-45 is 1: 4;
the ethylene propylene rubber raw rubber is Keltan 2750 produced by Langshen chemistry, and comprises the components of 48% of ethylene and 7.8% of ENB third monomer;
the addition ratio of the ethylene propylene rubber crude rubber Keltan 2750 to the vulcanization activator Ative CHO is 100: (4-6);
the addition ratio of the anti-aging agent 445 to the vulcanization activator Ative CHO is 1: (2-3).
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