A method for terminating and anti-aging after the polymerization reaction of synthetic rubber

Abstract

The present invention provides a method for terminating and anti-aging after the polymerization reaction of synthetic rubber, which comprises the following steps: adding a terminator solution, a non-ionic surfactant and an anti-aging agent to the polymerization reaction solution after the polymerization reaction of synthetic rubber in sequence and carrying out a stirring reaction. The method for terminating and anti-aging after the polymerization reaction provided by the present invention has less consumption of auxiliary agents, and the rubber product has good anti-aging performance. The method for terminating and anti-aging is to first add water or an alcohol solution, and then add substances such as a non-ionic surfactant and an anti-aging agent. This method for terminating and anti-aging can avoid the direct reaction between the residual catalyst that is not completely terminated and the anti-aging agent, and ensure that the synthetic rubber has good aging resistance. At the same time, this method for terminating and anti-aging has the characteristics of less consumption of auxiliary agents, no by-products, no pollution, environmental protection, etc., and can improve the stability of synthetic rubber products.

Description

Technical Field

[0001] The present invention belongs to the technical field of rubber, and particularly relates to a method for terminating and anti-aging after the polymerization reaction of synthetic rubber. Background Art

[0002] At present, the production of synthetic rubber mainly adopts the method of batch / continuous polymerization. After the polymerization is completed, a terminator, an anti-aging agent and an isolating agent are added to the reaction solution. The terminator and the anti-aging agent are generally added to the polymerization reaction solution at the same time. Since the viscosity of the rubber reaction solution is very high, it is difficult to stir and mix, and the reaction is difficult to terminate completely.

[0003] In the existing production technology, water or alcohol solution is generally selected as the terminator, that is, water or alcohol substances are added to the polymerization reaction solution as the terminator. In order to improve the aging resistance of rubber, an anti-aging agent is generally added. However, since both water and alcohol substances are polar substances, their compatibility with the non-polar polymer reaction solution is poor. Coupled with the particularly high viscosity of the polymerized rubber solution, many active centers are wrapped by macromolecular chains and cannot contact the terminator, so the reaction cannot be terminated completely, resulting in cross-linking between chemical bonds and even forming gels, seriously affecting the product quality. In this case, the catalyst residue is more likely to react with the anti-aging agent, consuming the anti-aging agent and reducing the aging resistance of the synthetic rubber product.

[0004] At present, in the production process of trans-butyl pentene rubber, when the polymerization system contains 0-25% solvent and the reaction conversion rate is 10%-30%, water or alcohol solution is used as the terminator for continuous production. This continuous process results in a shorter contact time between the terminator and the polymer molecules, increasing the difficulty of the terminator contacting the polymer molecular chains; at the same time, based on the equipment operation mode, the terminator and the anti-aging agent are added together, resulting in the termination reaction seriously affecting the oxidation effect of the anti-aging agent. Summary of the Invention

[0005] In view of this, the technical problem to be solved by the present invention is to provide a method for terminating and anti-aging after the polymerization reaction of synthetic rubber. The method provided by the present invention can effectively terminate the polymerization reaction and improve the aging resistance of rubber.

[0006] The present invention provides a method for terminating and anti-aging after the polymerization reaction of synthetic rubber, including the following steps:

[0007] After adding a terminator solution to the polymerization reaction solution after the polymerization reaction of synthetic rubber, a non-ionic surfactant and an anti-aging agent are added and stirred for reaction.

[0008] Preferably, the terminator solution is water, weakly alkaline water or alcohol solution.

[0009] Preferably, the ratio of the terminator solution to the total amount of polymers in the polymerization reaction solution is 0.1-10 wt%.

[0010] Preferably, the addition rate of the terminator solution is 0.1 - 5 g / (min·100 g of polymer).

[0011] Preferably, the non-ionic surfactant is alkoxypropylamine polyoxyethylene ether, and the antioxidant is a hindered phenol antioxidant.

[0012] Preferably, the ratio of the non-ionic surfactant to the total amount of polymer in the polymerization reaction solution is 0.5 - 1 wt%;

[0013] The dosage ratio of the antioxidant to the total amount of polymer in the polymerization reaction solution is 0.01 - 2 wt%.

[0014] Preferably, the addition rate of the non-ionic surfactant is 0.1 - 2 g / (min·100 g of polymer);

[0015] The addition rate of the antioxidant is 0.5 - 5 g / (min·100 g of polymer).

[0016] Preferably, the stirring speed is 1 - 200 revolutions per minute, preferably 100 - 150 revolutions per minute.

[0017] Preferably, the rubber polymerization reaction is carried out according to the following steps:

[0018] In the presence of a chain initiator and an olefin polymerization catalyst, the olefin is polymerized to obtain a polymerization reaction solution.

[0019] Preferably, the olefin is a C4 - C6 conjugated diene; the polymerization reaction solution contains 0 - 25% of a solvent; the olefin polymerization catalyst is one or more of the Ziegler - Natta system catalysts.

[0020] Compared with the prior art, the present invention provides a method for terminating and anti - aging after the polymerization reaction of synthetic rubber, including the following steps: successively adding a terminator solution, a non - ionic surfactant, and an antioxidant to the polymerization reaction solution after the polymerization reaction of synthetic rubber and stirring for reaction. The method for terminating and anti - aging after the polymerization reaction provided by the present invention uses less auxiliary agents, and the rubber product has good anti - aging performance. The method for terminating and anti - aging is to first add water or an alcohol solution, and then add substances such as a non - ionic surfactant and an antioxidant. This method for terminating and anti - aging can avoid the direct reaction of the unreacted completely residual catalyst with the antioxidant, ensuring that the synthetic rubber has good aging resistance. At the same time, this method for terminating and anti - aging has the characteristics of less auxiliary agent consumption, no by - products, no pollution, environmental protection, etc., and can improve the stability of the synthetic rubber product. Description of the Drawings

[0021] Figure 1 It is a curve of torque S' changing with time;

[0022] Figure 2 To terminate water addition to improve product color comparison;

[0023] Figure 3 The addition sequence of the terminator and antioxidant affects color change;

[0024] Figure 4 For the torque S' vs. time curve;

[0025] Figure 5 Schematic process flow diagram for simultaneous injection of terminator and antioxidant;

[0026] Figure 6 Schematic process flow diagram for sequential addition of terminator, non-ionic surfactant and antioxidant;

[0027] Figure 7 For the modulus change of TBIR before and after aging at 150°C;

[0028] Figure 8 For the color change of TBIR during thermal-oxidative aging at 100°C. Detailed implementation mode

[0029] The present invention provides a method for terminating and antioxidant addition after a synthetic rubber polymerization reaction, comprising the following steps:

[0030] A terminator solution, a non-ionic surfactant and an antioxidant are sequentially added to the polymerization reaction liquid after the synthetic rubber polymerization reaction, and stirred for reaction.

[0031] The present invention first prepares a polymerization reaction liquid after a synthetic rubber polymerization reaction, wherein the rubber polymerization reaction is carried out according to the following steps:

[0032] In the presence of a chain initiator and an olefin polymerization catalyst, an olefin is subjected to a polymerization reaction to obtain a polymerization reaction liquid.

[0033] In the present invention, the olefin is a conjugated diene of C4-C6, preferably one or more of butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene and 2,3-dimethylbutadiene, and most preferably isoprene and butadiene;

[0034] The olefin polymerization catalyst is one or more of Ziegler-Natta system catalysts.

[0035] The chain initiator is selected from alkyl aluminums, preferably triisobutyl aluminum or diisobutyl aluminum chloride, and further preferably triisobutyl aluminum.

[0036] In the present invention, according to the method of the present invention, preferably, the polymerization reaction liquid with termination and anti-aging contains 0 to 25% by mass of a solvent. The solvent is selected from propane, hexane or xylene, preferably hexane;

[0037] In the present invention, the olefin polymerization conditions can be a conventional selection in the art. For the present invention, preferably, the olefin polymerization conditions include a polymerization temperature of 20 to 80 °C, preferably 20, 30, 40, 50, 60, 70, 80, or any value between 20 and 80 °C, and a polymerization pressure of 0.1 to 0.5 MPa, preferably 0.1, 0.2, 0.3, 0.4, 0.5, or any value between 0.1 and 0.5 MPa.

[0038] The method of the present invention is suitable for batch polymerization and also suitable for continuous polymerization, among which, it is particularly suitable for continuous polymerization. In this way, the polymerization reaction can be terminated completely, the volatile matter can be reduced, the rubber quality can be improved, and the losses of auxiliary materials, equipment and energy can be reduced.

[0039] After obtaining the polymerization reaction liquid, in order to terminate the reaction and prevent the product from aging, a terminator solution, a non-ionic surfactant and an anti-aging agent are sequentially added to the polymerization reaction liquid and stirred for reaction.

[0040] Among them, the terminator solution is water, weakly alkaline water or an alcohol solution. The pH of the weakly alkaline water is 8 to 9, and the alcohol solution is selected from monohydric alcohols, preferably ethanol.

[0041] Preferably, the terminator solution is high-purity water without impurities. Using this method to terminate the rubber polymerization reaction has the characteristics of high environmental protection, small dosage, no by-products, no pollution, etc.

[0042] The ratio of the terminator solution to the total amount of polymers in the polymerization reaction liquid is 0.1 to 10 wt%, preferably 0.1 wt%, 0.5 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, or any value between 0.1 and 10 wt%.

[0043] The addition rate of the terminator solution is 0.1 to 5 g / (min·100 g of polymer), preferably 0.1, 0.5, 1, 2, 3, 4, 5, or any value between 0.1 and 5 g / (min·100 g of polymer).

[0044] According to the method of the present invention, preferably, based on pure water, the dosage of the terminator solution is not less than the amount of active centers in the polymers in the reaction liquid to be terminated, and can be specifically selected according to needs.

[0045] After adding the terminator solution, the reaction is terminated, and then a non-ionic surfactant and an antioxidant are added for stirring reaction.

[0046] By first adding a terminator and then adding a non-ionic surfactant and an antioxidant, the method of the present invention can effectively terminate the reaction, completely avoid the reaction between the un-terminated catalyst residue and the antioxidant, improve the aging resistance of the rubber after termination and antioxidant addition, and improve the product quality.

[0047] Among them, the non-ionic surfactant is alkoxypropylamine polyoxyethylene ether, and more preferably fatty acid polyoxyethylene ester. On the basis of adding the terminator solution, the active centers Ti and Al in the polymerization reaction are further terminated by the non-ionic surfactant.

[0048] The dosage ratio of the non-ionic surfactant to the total amount of polymers in the polymerization reaction solution is 0.5 wt% - 1 wt%, preferably 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1.0 wt%, or any value between 0.5 wt% - 1 wt%.

[0049] The addition rate of the non-ionic surfactant is 0.1 - 2 g / (min·100 g polymer), preferably 0.1, 0.5, 1, 1.5, 2, or any value between 0.1 - 2 g / (min·100 g polymer).

[0050] According to the method of the present invention, the optional range of the antioxidant substances is relatively wide. The antioxidant substances are hindered phenol antioxidants. For the present invention, the antioxidant is preferably one or more of isooctyl 3,5 - di - tert - butyl - 4 - hydroxybenzenepropionate (antioxidant 1135), 4,6 - dioctylthiomethyl - o - cresol (antioxidant 1520), 2,6 - di - tert - butyl - 4 - methylphenol (antioxidant 264), and n - octadecyl 3 - (3,5 - di - tert - butyl - 4 - hydroxyphenyl) propionate (antioxidant 1076) and other compound antioxidants. In this way, the reaction between the un-terminated active centers and the catalyst residue and the antioxidant is avoided, the aging resistance of the rubber after termination and antioxidant addition is improved, and the product quality is improved.

[0051] In the present invention, the organic solvent for dissolving the hindered phenol antioxidant is isoprene, which is convenient for subsequent separation.

[0052] In the present invention, the dosage ratio of the antioxidant to the total amount of polymers in the polymerization reaction solution is 0.01 - 2 wt%, preferably 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, or any value between 0.01 - 2 wt%.

[0053] The addition rate of the antioxidant is 0.5 - 5 g / (min·100 g of polymer), preferably 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, or any value between 0.5 - 5 g / (min·100 g of polymer).

[0054] In the present invention, the non-ionic surfactant and the antioxidant are added to the polymerization reaction solution under stirring conditions, and the stirring speed is 1 - 200 revolutions per minute, preferably 1, 5, 10, 50, 100, 150, 200, or any value between 1 - 200 revolutions per minute.

[0055] In the present invention, the non-ionic surfactant and the antioxidant can be added to the polymerization reaction solution simultaneously.

[0056] In the present invention, the terminator solution is added to the polymerization reactor and the post-treatment connection device through the terminator solution inlet, and the non-ionic surfactant and the antioxidant are added to the polymerization reactor and the post-treatment connection device through the antioxidant inlet.

[0057] Among them, the terminator solution inlet is arranged at the upstream position of the material flow of the antioxidant inlet to ensure that the polymerization reaction solution reacts with the terminator solution first and then reacts with the non-ionic surfactant and the antioxidant.

[0058] The polymerization reactor and the post-treatment connection device are pipeline devices with a mixing and stirring function, preferably a screw stirrer, and more preferably a double-rotor stirrer.

[0059] The above method can avoid the reaction of incompletely terminated active centers and catalyst residues with the antioxidant, improve the aging resistance of the rubber after termination and antioxidant addition, and improve the product quality.

[0060] In the present invention, the Shore hardness is measured according to the Shore hardness tester method (Shore hardness) GB / T 531.1 - 2008, the tensile strength, elongation at break, 100% and 300% modulus at 100% elongation are measured according to the test methods specified in GB / T 528 - 2009, the tear strength is measured according to the test methods specified in GB / T 529 - 2008, the resilience is tested according to the test methods specified in GB / T 1681 - 2009, and the DIN abrasion is tested according to the test methods specified in the standard GB / T 9867.

[0061] In the present invention, the monomer conversion rate is the percentage of the weight of isoprene and butadiene added to the weight of the trans-1,4-butadiene-isoprene copolymer rubber obtained after polymerization.

[0062] To further understand the present invention, the termination and anti-aging method after the synthetic rubber polymerization reaction provided by the present invention will be described below in conjunction with embodiments. The protection scope of the present invention is not limited by the following embodiments.

[0063] Example 1

[0064] (1) The polymerization catalyst is a magnesium chloride-titanium tetrachloride catalyst, and the active component is TiCl 4 , and its mass fraction is 30% of the solvent. The co-catalyst is triisobutylaluminum Al(i-Bu) 3 , the solvent is hexane, and the molar ratio of Ti / isoprene is 1.5x10 -5 :1. Control the polymerization temperature at 40°C and the polymerization pressure at 0.2 Mpa. After the polymerization is stable, a polymerization reaction solution is obtained.

[0065] (2) Under stirring conditions, the stirring conditions include: a stirring speed of 150 r / min. First, add 1 wt% of water to the polymerization reaction solution from the terminator inlet. After termination, add a hexane solution of 1 wt% of thioether-type hindered phenol antioxidant 1134 (a compound antioxidant, hereinafter referred to as antioxidant 1134 for short) from the antioxidant inlet. The addition speed is 0.2 g / (min·100 g polymer). The physical property characterization results and anti-aging results of the polymer after the glue solution is coagulated and dried are shown in Table 1 and Figure 1 .

[0066] Comparative Example 1-1

[0067] Step (1) is the same as that in Example 1. The difference is that in step (2), the terminator and antioxidant 1134 are added simultaneously, and the other conditions are the same. The physical property characterization results and anti-aging results of the polymer after the glue solution is coagulated and dried are shown in Table 1 and Figure 1 .

[0068] Comparative Example 1-2

[0069] Step (1) is the same as that in Example 1. The difference is that in step (2), the terminator is changed to an ethanol solution with a concentration of 100%, and it is added simultaneously with antioxidant 1134, and the other conditions are the same. The physical property characterization results and anti-aging results of the polymer after the glue solution is coagulated and dried are shown in Table 1 and Figure 1 .

[0070] Table 1 Performance Comparison

[0071]

[0072] As can be seen from the data in Table 1, the mechanical properties and other performance indicators of the rubber obtained in Example 1 and Comparative Example 1-1 are roughly equivalent, but the heat aging resistance performance shows an obvious difference (simulating the anaerobic aging process by MDR scanning test, 150 °C * 10 min, strain 14%, frequency 1.67 Hz). At 150 °C, the torque of the test curve of the rubber obtained in Example 1 did not show an obvious decrease, while the torque of the test curve obtained in Comparative Example 1-1 showed a decreasing trend, indicating that the molecular chains in Comparative Example 1 degraded and the anaerobic aging resistance performance was poor. Although the terminator in Comparative Example 1-1 is water, but water and antioxidant are added simultaneously, and the compatibility of the antioxidant with the rubber solution is much higher than that of water. Therefore, a large amount of phenol titanium is formed, which will react with the thioether-type antioxidant to promote the thermal decomposition of the rubber. This shows that the method of adding the terminator (water) first and then the antioxidant in the present invention can avoid the direct reaction of the un-terminated completely catalyst residue with the antioxidant, and improve the aging resistance performance of the terminated polymer.

[0073] At the same time, as can be seen from the data in Table 1, the performance of the rubber obtained in Comparative Example 1-2 is significantly inferior to that of Example 1 in terms of resilience, DIN abrasion and loss factor, and the difference in anaerobic aging resistance performance at 120 °C is also obvious. At 120 °C, compared with Example 1, the torque of the test curve obtained in Comparative Example 1-2 is lower and shows a decreasing trend from the beginning, indicating that the molecular chains in Comparative Example 2 are more likely to undergo aging degradation. The terminator in Comparative Example 1-2 is an ethanol solution, and its catalyst termination product is theoretically Ti(OC 2 H 5 ) 4 , which is itself the main catalyst of trans rubber and has a high reaction activity. It synergistically acts with the thioether-type hindered phenol antioxidant to release free radicals, causing the degradation of TBIR. This shows that the terminator solution of the present invention is preferably pure water.

[0074] Furthermore, adding water can improve the color problem of the product appearance. As Figure 2 shown, the process of adding water to terminate first and then adding the antioxidant can improve the problem of yellowing of the product color and further improve the product quality. In the small-scale experiment, as Figure 3 shown, implemented according to the addition sequence of titanium tetrachloride → water → antioxidant, adding 100 ppm of titanium tetrachloride hexane solution into the Schlenk flask, adding 1% of water first, and then adding the 1134 hexane solution prepared into 0.3%, the color did not turn yellow (left figure), while adding water and antioxidant solution simultaneously, the color turned yellow significantly (right figure). This shows that the method of adding the terminator (water) first and then the antioxidant in the present invention not only improves the aging resistance performance of the terminated polymer, but also can improve the problem of yellowing of the polymer product color.

[0075] Example 2

[0076] (1) The polymerization catalyst is a magnesium chloride - titanium tetrachloride catalyst, and the active component is TiCl 4 , and its mass fraction is 30% of the solvent. The solvent is hexane, and the molar ratio of Ti / isoprene is 1.5x10 -5 :1. The polymerization temperature is controlled at 40 °C, and the polymerization pressure is 0.2 Mpa. After the polymerization is stable, a reaction solution is obtained.

[0077] (2) Under stirring conditions, the stirring conditions include a stirring speed of 150 r / min. First, 1 wt% of water is added to the polymerization reaction solution from the terminator inlet. After termination, a 0.05 wt% hexane solution of antioxidant 1135 is added from the antioxidant inlet at a rate of 1 g / (min·100 g polymer). The physical property characterization results and anti - aging results of the polymer after the glue solution is coagulated and dried are shown in Table 2 and Figure 4 .

[0078] Comparative Example 2 - 1

[0079] Step (1) is the same as that of Example 2, except that in step (2), antioxidant 1135 is changed to antioxidant 1134, and the other conditions are the same. The physical property characterization results and anti - aging results of the polymer after the glue solution is coagulated and dried are shown in Table 2 and Figure 4 .

[0080] Table 2 Performance Comparison

[0081]

[0082] It can be seen from the data in Table 2 that the comprehensive performance indicators of the rubber obtained in Example 2 are better than those of Comparative Example 2 - 1. From the MDR torque curve, it can be known that although the initial torque of Example 2 and Comparative Example 2 - 1 is quite the same, the torque value of Comparative Example 2 - 1 decreases more significantly with time, and its anaerobic aging resistance performance is relatively poor. Both Example 2 and Comparative Example 2 - 1 first add a terminator, and both are water. The difference lies in the type of antioxidant. The type of antioxidant in the present invention is a hindered phenol antioxidant, preferably a non - thioether type hindered phenol antioxidant.

[0083] Example 3

[0084] (1) The polymerization catalyst is a magnesium chloride - titanium tetrachloride catalyst, and the active component is TiCl 4 , and its mass fraction is 30% of the solvent. The solvent is hexane, and the molar ratio of Ti / isoprene is 1.5x10 -5 :1. The polymerization temperature is controlled at 40 °C, and the polymerization pressure is 0.2 Mpa. Polymerization is carried out for 2.5 h to obtain a polymerization solution with a solid content of 15%.

[0085] (2) The termination device adopts a twin-screw mode, with a rotation speed of 150 rpm and a polymerization liquid flow rate of 1000 kg / h. Water is injected at a flow rate of 4 kg / h from the terminator inlet, and at the same time, a hexane solution of antioxidant 1135 with a concentration of 0.05 wt% is injected at a flow rate of 1 kg / h from the antioxidant inlet. The specific process is as Figure 5 shown. The rubber solution is passed through a devolatilization and drying system to obtain the corresponding polymer.

[0086] Comparative Example 3-1

[0087] Step (1) is the same as that in Example 3.

[0088] In step (2), the termination device adopts a twin-screw mode, with a rotation speed of 150 rpm and a polymerization liquid flow rate of 1000 kg / h. Water is injected at a flow rate of 4 kg / h from the terminator inlet, and at the same time, a non-ionic surfactant alkoxypropylamine polyoxyethylene ether solution of antioxidant 1135 with a concentration of 0.05 wt% is injected at a flow rate of 1 kg / h. The antioxidant inlet is moved back 30 cm (the specific process is as Figure 6 ), and the material is mixed with the terminator and then with antioxidant 1135.

[0089] The physical property characterization results and anti-aging results are shown in Table 3.

[0090] Table 3 Performance Comparison

[0091]

[0092] It can be found through comparison that after using the non-ionic surfactant, the fatigue resistance of the product after aging is significantly improved.

[0093] Example 4

[0094] In step (1), the polymerization catalyst is a magnesium chloride-titanium tetrachloride catalyst, the active component is TiCl4, its mass fraction is 30% of the solvent, the solvent is hexane, the molar ratio of Ti / isoprene is 1.5x10-5:1, the polymerization temperature is controlled at 40 °C, the polymerization pressure is 0.2 Mpa, and the polymerization is carried out for 2.5 h to obtain a polymerization liquid with a solid content of 15%.

[0095] In step (2), the termination device adopts a twin-screw mode, with a rotation speed of 150 rpm and a polymerization liquid flow rate of 1000 kg / h. Water is injected at a flow rate of 4 kg / h from the terminator inlet, and at the same time, solutions (B-24, B-25, B-27) with the following configurations are injected at a flow rate of 1 kg / h from the antioxidant inlet respectively. The specific process is as Figure 5 shown. The rubber solution is passed through a devolatilization and drying system to obtain the corresponding polymer.

[0096] Solution preparation method:

[0097] B-24 (1 g of antioxidant 1135 is added to every 10 ml of ethanol);

[0098] B-25 (1 g of antioxidant 1135 is added to every 10 ml of water);

[0099] B-27 (1.1 g of antioxidant 1135 is added to every 10 ml of non-ionic surfactant alkoxypropylamine polyoxyethylene ether).

[0100] RPA tests were carried out on the TBIR samples before and after aging (150 °C, 48 h) to investigate the change in their modulus. RPA strain sweep test conditions: 100 °C, preheating for 3.0 min, testing at 100 °C, strain range 0.1 - 100%, frequency 1 Hz.

[0101] The experimental results are as Figure 7 shown. Figure 7 In the figure, "TBIR-B-27" represents (1.1 g of antioxidant 1135 is added to every 10 ml of non-ionic surfactant), "TBIR-B-25" represents (1 g of antioxidant 1135 is added to every 10 ml of water), and "TBIR-B-24" represents (1 g of antioxidant 1135 is added to every 10 ml of ethanol);

[0102] From Figure 7 the analysis, it can be seen that the TBIR-27 and TBIR-27Y (Y - ethanol precipitation) synthesized with non-ionic surfactant have the best aging stability, and the modulus does not decrease significantly with strain under large strain.

[0103] Example 5

[0104] For the TBIR thermal oxidation aging experiment, 5 g of each of the synthetic products obtained in each step (1) of Examples 1 - 4 were taken and placed in an oven at 150 °C. The color change and degradation of the TBIR raw rubber were observed every 0.5 h. The changes of the samples in the 150 °C oven are as follows Figure 8 shown.

[0105] From the above experimental results, it can be seen that when not aged, compared with the samples using other terminators, the sample with water as the terminator has a relatively whiter color; when aged at 150 °C for 0.5 h, the color of the sample has changed slightly; when aged for 1 h, the sample is significantly yellowed and shows the phenomenon of aging degradation and stickiness; when aged for 2 h, the color deepens, but the change range is not very obvious. Considering the whole aging process, the sample using non-ionic surfactant simultaneously has the smallest degree of color change.

[0106] The above is only the preferred implementation mode of the present invention. It should be pointed out that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and retouches can still be made, and these improvements and retouches should also be regarded as the protection scope of the present invention.

Claims

1. A method for terminating and anti-aging after the polymerization reaction of synthetic rubber, characterized in that, it comprises the following steps: After adding a terminator solution to the polymerization reaction liquid after the polymerization reaction of synthetic rubber, a non-ionic surfactant and an anti-aging agent are added and stirred for reaction, and the non-ionic surfactant is alkoxypropylamine polyoxyethylene ether.

2. The method according to claim 1, characterized in that, the terminator solution is water or an alcohol solution.

3. The method according to claim 1, characterized in that, the ratio of the terminator solution to the total amount of polymers in the polymerization reaction liquid is 0.1-10 wt%.

4. The method according to claim 1, characterized in that, the addition rate of the terminator solution is 0.1-5 g / (min·100 g of polymer).

5. The method according to claim 1, characterized in that, the anti-aging agent is a hindered phenol anti-aging agent.

6. The method according to claim 1, characterized in that, the ratio of the non-ionic surfactant to the total amount of polymers in the polymerization reaction liquid is 0.5-1 wt%; the dosage of the anti-aging agent is 0.01-2 wt% based on the total amount of polymers in the polymerization reaction liquid.

7. The method according to claim 1, characterized in that, the addition rate of the non-ionic surfactant is 0.1-2 g / (min·100 g of polymer); the addition rate of the anti-aging agent is 0.5-5 g / (min·100 g of polymer).

8. The method according to claim 1, characterized in that, the stirring speed is 1-200 revolutions per minute.

9. The method according to claim 8, characterized in that, the stirring speed is 100-150 revolutions per minute.

10. The method according to claim 1, characterized in that, the rubber polymerization reaction is carried out according to the following steps: In the presence of a chain initiator and an olefin polymerization catalyst, olefins are polymerized to obtain a polymerization reaction liquid.

11. The method according to claim 10, characterized in that, the olefin is a conjugated diene of C4-C6; the polymerization reaction liquid contains 0-25% of a solvent; the olefin polymerization catalyst is one or more of the Ziegler-Natta system catalysts.

Images